Pesticidal compositions and processes related thereto

ABSTRACT

This document discloses molecules having the following formulas (“Formula One” &amp;“Formula Two” and “Formula Three”) 
     
       
         
         
             
             
         
       
         
         
           
             The Ar 1 , Het, Ar 2 , R1, R2, R3, R4, and R5 are further described herein.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority from U.S. provisional application61/594,107 filed on Feb. 2, 2012. The entire content of this provisionalapplication is hereby incorporated by reference into this Application.

FIELD OF THE INVENTION

The invention disclosed in this document is related to the field ofprocesses to produce molecules that are useful as pesticides (e.g.,acaricides, insecticides, molluscicides, and nematicides), suchmolecules, and processes of using such molecules to control pests.

BACKGROUND OF THE INVENTION

Pests cause millions of human deaths around the world each year.Furthermore, there are more than ten thousand species of pests thatcause losses in agriculture. The world-wide agricultural losses amountto billions of U.S. dollars each year.

Termites cause damage to all kinds of private and public structures. Theworld-wide termite damage losses amount to billions of U.S. dollars eachyear.

Stored food pests eat and adulterate stored food. The world-wide storedfood losses amount to billions of U.S. dollars each year, but moreimportantly, deprive people of needed food.

There is an acute need for new pesticides. Certain pests are developingresistance to pesticides in current use. Hundreds of pest species areresistant to one or more pesticides. The development of resistance tosome of the older pesticides, such as DDT, the carbamates, and theorganophosphates, is well known, but resistance has even developed tosome of the newer pesticides.

Therefore, for many reasons, including the above reasons, a need existsfor new pesticides.

DEFINITIONS

The examples given in the definitions are generally non-exhaustive andmust not be construed as limiting the invention disclosed in thisdocument. It is understood that a substituent should comply withchemical bonding rules and steric compatibility constraints in relationto the particular molecule to which it is attached.

“Acaricide Group” is defined under the heading “ACARICIDES”.

“AI Group” is defined after the place in this document where the“Herbicide Group” is defined.

“Alkenyl” means an acyclic, unsaturated (at least one carbon-carbondouble bond), branched or unbranched, substituent consisting of carbonand hydrogen, for example, vinyl, allyl, butenyl, pentenyl, and hexenyl.

“Alkenyloxy” means an alkenyl further consisting of a carbon-oxygensingle bond, for example, allyloxy, butenyloxy, pentenyloxy, hexenyloxy.

“Alkoxy” means an alkyl further consisting of a carbon-oxygen singlebond, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy,isobutoxy, and tert-butoxy.

“Alkyl” means an acyclic, saturated, branched or unbranched, substituentconsisting of carbon and hydrogen, for example, methyl, ethyl, propyl,isopropyl, butyl, and tert-butyl.

“Alkynyl” means an acyclic, unsaturated (at least one carbon-carbontriple bond), branched or unbranched, substituent consisting of carbonand hydrogen, for example, ethynyl, propargyl, butynyl, and pentynyl.

“Alkynyloxy” means an alkynyl further consisting of a carbon-oxygensingle bond, for example, pentynyloxy, hexynyloxy, heptynyloxy, andoctynyloxy.

“Aryl” means a cyclic, aromatic substituent consisting of hydrogen andcarbon, for example, phenyl, naphthyl, and biphenyl.

“Cycloalkenyl” means a monocyclic or polycyclic, unsaturated (at leastone carbon-carbon double bond) substituent consisting of carbon andhydrogen, for example, cyclobutenyl, cyclopentenyl, cyclohexenyl,norbornenyl, bicyclo[2.2.2]octenyl, tetrahydronaphthyl,hexahydronaphthyl, and octahydronaphthyl.

“Cycloalkenyloxy” means a cycloalkenyl further consisting of acarbon-oxygen single bond, for example, cyclobutenyloxy,cyclopentenyloxy, norbornenyloxy, and bicyclo[2.2.2]octenyloxy.

“Cycloalkyl” means a monocyclic or polycyclic, saturated substituentconsisting of carbon and hydrogen, for example, cyclopropyl, cyclobutyl,cyclopentyl, norbornyl, bicyclo[2.2.2]octyl, and decahydronaphthyl.

“Cycloalkoxy” means a cycloalkyl further consisting of a carbon-oxygensingle bond, for example, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy,norbornyloxy, and bicyclo[2.2.2]octyloxy.

“Fungicide Group” is defined under the heading “FUNGICIDES.”

“Halo” means fluoro, chloro, bromo, and iodo.

“Haloalkoxy” means an alkoxy further consisting of, from one to themaximum possible number of identical or different, halos, for example,fluoromethoxy, trifluoromethoxy, 2,2-difluoropropoxy, chloromethoxy,trichloromethoxy, 1,1,2,2-tetrafluoroethoxy, and pentafluoroethoxy.

“Haloalkyl” means an alkyl further consisting of, from one to themaximum possible number of, identical or different, halos, for example,fluoromethyl, trifluoromethyl, 2,2-difluoropropyl, chloromethyl,trichloromethyl, and 1,1,2,2-tetrafluoroethyl.

“Herbicide Group” is defined under the heading “HERBICIDES.”

“Heterocyclyl” means a cyclic substituent that may be fully saturated,partially unsaturated, or fully unsaturated, where the cyclic structurecontains at least one carbon and at least one heteroatom, where saidheteroatom is nitrogen, sulfur, or oxygen. Examples of aromaticheterocyclyls include, but are not limited to, benzofuranyl,benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, benzothienyl,benzothiazolyl cinnolinyl, furanyl, indazolyl, indolyl, imidazolyl,isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, oxadiazolyl,oxazolinyl, oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl, pyrazolyl,pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl,quinoxalinyl, tetrazolyl, thiazolinyl, thiazolyl, thienyl, triazinyl,and triazolyl. Examples of fully saturated heterocyclyls include, butare not limited to, piperazinyl, piperidinyl, morpholinyl, pyrrolidinyl,tetrahydrofuranyl, and tetrahydropyranyl. Examples of partiallyunsaturated heterocyclyls include, but are not limited to,1,2,3,4-tetrahydro-quinolinyl, 4,5-dihydro-oxazolyl,4,5-dihydro-1H-pyrazolyl, 4,5-dihydro-isoxazolyl, and2,3-dihydro-[1,3,4]-oxadiazolyl.

“Insecticide Group” is defined under the heading “INSECTICIDES.”

“Nematicide Group” is defined under the heading “NEMATICIDES”

“Synergist Group” is defined under the heading “SYNERGISTIC MIXTURES ANDSYNERGISTS”

DETAILED DESCRIPTION OF THE INVENTION

This document discloses molecules having the following formulas(“Formula One” &“Formula Two” and “Formula Three”): (In the followingformulas the nitrogens are numbered 1, 2, and 3, solely for the purposeof identifying them and being able to refer to them throughout thisdocument for clarity purposes)

wherein:

(a) Ar₁ is

-   -   (1) furanyl, phenyl, pyridazinyl, pyridyl, pyrimidinyl, thienyl,        or    -   (2) substituted furanyl, substituted phenyl, substituted        pyridazinyl, substituted pyridyl, substituted pyrimidinyl, or        substituted thienyl,        -   wherein said substituted furanyl, substituted phenyl,            substituted pyridazinyl, substituted pyridyl, substituted            pyrimidinyl, and substituted thienyl, have one or more            substituents independently selected from H, F, Cl, Br, I,            CN, NO₂, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆ cycloalkyl,            C₃-C₆ halocycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆            halocycloalkoxy, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆            alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl),            S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆            haloalkyl), C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y),            C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆            haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆            cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),            C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆            alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl),            phenyl, phenoxy, substituted phenyl, and substituted            phenoxy,        -   wherein such substituted phenyl and substituted phenoxy have            one or more substituents independently selected from H, F,            Cl, Br, I, CN, NO₂, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆            cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆            halocycloalkoxy, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆            alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl),            S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆            haloalkyl), C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y),            C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆            haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆            cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),            C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆            alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl)            phenyl, and phenoxy;

(b) Het is a 5 or 6 membered, saturated or unsaturated, heterocyclicring, containing one or more heteroatoms independently selected fromnitrogen, sulfur, or oxygen, and where Ar₁ and Ar₂ are not ortho to eachother (but may be meta or para, such as, for a five membered ring theyare 1,3 and for a 6 membered ring they are either 1,3 or 1,4), and wheresaid heterocyclic ring may also be substituted with one or moresubstituents independently selected from H, F, Cl, Br, I, CN, NO₂, oxo,C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl,C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy, C₁-C₆ alkoxy, C₁-C₆haloalkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl),S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl),C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl),C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆ haloalkyl),C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, phenoxy,substituted phenyl and substituted phenoxy,

-   -   wherein such substituted phenyl and substituted phenoxy have one        or more substituents independently selected from H, F, Cl, Br,        I, CN, NO₂, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆ cycloalkyl,        C₃-C₆ halocycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy,        C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl,        S(═O)_(n)(C₁-C₆ alkyl), S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆        alkyl), OSO₂(C₁-C₆ haloalkyl), C(═O)H, C(═O)NR_(x)R_(y), (C₁-C₆        alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl),        C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆        cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),        C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆        alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl),        phenyl, and phenoxy;

(c) Ar₂ is

-   -   (1) furanyl, phenyl, pyridazinyl, pyridyl, pyrimidinyl, thienyl,        or    -   (2) substituted furanyl, substituted phenyl, substituted        pyridazinyl, substituted pyridyl, substituted pyrimidinyl, or        substituted thienyl,        -   wherein said substituted furanyl, substituted phenyl,            substituted pyridazinyl, substituted pyridyl, substituted            pyrimidinyl, and substituted thienyl, have one or more            substituents independently selected from H, F, Cl, Br, I,            CN, NO₂, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆ cycloalkyl,            C₃-C₆ halocycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆            halocycloalkoxy, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆            alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl),            S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆            haloalkyl), C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y),            C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆            haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆            cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),            C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆            alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl),            phenyl, phenoxy, substituted phenyl and substituted phenoxy,        -   wherein such substituted phenyl and substituted phenoxy have            one or more substituents independently selected from H, F,            Cl, Br, I, CN, NO₂, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆            cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆            halocycloalkoxy, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆            alkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl),            S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆            haloalkyl), C(═O)H, C(═O)NR_(x)R_(y), (C₁-C₆            alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl),            C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆            cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₁-C₆            haloalkyl), C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆ alkenyl),            (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆ alkyl),            C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, and phenoxy;

(d) R1 is selected from H, CN, F, Cl, Br, I, C₁-C₆ alkyl, C₃-C₆cycloalkyl, C₃-C₆ cycloalkoxy, C₁-C₆ alkoxy, C₂-C₆ alkenyl, C₂-C₆alkynyl, S(═O)_(n)(C₁-C₆ alkyl), OSO₂(C₁-C₆ alkyl), C(═O)NR_(x)R_(y),(C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl),C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, or phenoxy,

-   -   wherein each alkyl, cycloalkyl, cycloalkoxy, alkoxy, alkenyl,        alkynyl, phenyl, and phenoxy, are optionally substituted with        one or more substituents independently selected from F, Cl, Br,        I, CN, NO₂, oxo, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆ cycloalkyl,        C₃-C₆ halocycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy,        C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl,        S(═O)_(n)(C₁-C₆ alkyl), S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆        alkyl), OSO₂(C₁-C₆ haloalkyl), C(═O)NR_(x)R_(y), (C₁-C₆        alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl),        C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆        cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),        C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆        alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl),        phenyl, and phenoxy;

(e) R2 is H, C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl, C₂-C₆alkynyl, C(═O)H, C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl), C(═O)(C₃-C₆cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, C₁-C₆alkylphenyl, C₁-C₆ alkyl-O-phenyl, C(═O)Het-1, Het-1, C₁-C₆ alkylHet-1,or C₁-C₆ alkyl-O-Het-1,

-   -   wherein each alkyl, cycloalkyl, alkenyl, alkynyl, phenyl, and        Het-1 are optionally substituted with one or more substituents        independently selected from F, Cl, Br, I, CN, NO₂, NR_(x)R_(y),        C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆ cycloalkyl, C₃-C₆        halocycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy, C₁-C₆        alkoxy, C₁-C₆ haloalkoxy, C₂-C₆ alkenyl, C₃-C₆ cycloalkenyl,        C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl), S(═O)_(n)(C₁-C₆        haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl), C(═O)H,        C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl),        C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆        haloalkyl), C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl),        C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆ alkenyl), (C₁-C₆        alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆        alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, phenoxy, and Het-1;

(f) R3 is C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl,C(═O)H, C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl), C(═O)(C₃-C₆cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, C₁-C₆alkylphenyl, C₁-C₆ alkyl-O-phenyl, C(═O)Het-1, Het-1, C₁-C₆ alkylHet-1,C₁-C₆ alkyl-O—C(═O)C₁-C₆ alkyl-O—C₁-C₆ alkyl, C₁-C₆ alkyl-O—C(═O)C₁-C₆alkyl-O—C₁-C₆ alkyl-O—C₁-C₆ alkyl, C₁-C₆ alkyl-O—C(═O)C₁-C₆alkyl-O—C₁-C₆ haloalkyl, C₁-C₆ alkyl-O—C(═O)C₁-C₆alkyl-N(R_(x))C(═O)—O-phenyl, C₁-C₆ alkyl-O—C(═O)C₁-C₆alkyl-N(R_(X))C(═O)—O—C₁-C₆ alkylphenyl, C₁-C₆ alkylC(═O)N(R_(x))C₁-C₆alkyl, C₁-C₆ alkylC(═O)N(R_(x))C₁-C₆ alkylHet-1C(═O)—O—C₁-C₆ alkyl,C₁-C₆ alkylC(═O)N(R_(x))C₁-C₆ alkylHet-1, C₁-C₆ alkylC(═O)Het-1, C₁-C₆alkylC(═O)N(R_(x))C₁-C₆ alkyl(N(R_(x))(R_(y)))(C(═O)OH), C₁-C₆alkylC(═O)N(R_(x))C₁-C₆ alkylN(R_(x))(R_(y)), C₁-C₆alkylC(═O)N(R_(x))C₁-C₆ alkylN(R_(x))C(═O)—O—C₁-C₆ alkyl, C₁-C₆alkylC(═O)N(R_(x))C₁-C₆ alkyl(N(R_(x))C(═O)—O—C₁-C₆ alkyl)(C(═O)OH),C₁-C₆ alkylC(═O)Het-1C(═O)—O—C₁-C₆ alkyl, C₁-C₆ alkyl-O—C(═O)—O—C₁-C₆alkyl, C₁-C₆ alkyl-O—C(═O)C₁-C₆ alkyl, C₁-C₆ alkyl-O—C(═O)C₃-C₆cycloalkyl, C₁-C₆ alkyl-O—C(═O)Het-1, C₁-C₆ alkyl-O—C(═O)C₁-C₆alkyl-N(R_(X))C(═O)—O—C₁-C₆ alkyl, C₁-C₆ alkyl-NR_(x)R_(y), or C₁-C₆alkyl-O-Het-1,

-   -   wherein each alkyl, cycloalkyl, alkenyl, alkynyl, phenyl, and        Het-1 are optionally substituted with one or more substituents        independently selected from F, Cl, Br, I, CN, NO₂, NR_(x)R_(y),        C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆ cycloalkyl, C₃-C₆        halocycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy, C₁-C₆        alkoxy, C₁-C₆ haloalkoxy, C₂-C₆ alkenyl, C₃-C₆ cycloalkenyl,        C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl), S(═O)_(n)(C₁-C₆        haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl), C(═O)H,        C(═O)OH, C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆        alkyl), C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆ haloalkyl),        C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆        cycloalkyl), C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆ alkenyl), (C₁-C₆        alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆        alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, phenoxy, Si(C₁-C₆ alkyl)₃,        S(═O)_(n)NR_(x)R_(y), and Het-1;

(g) R₄ is H, C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl, C₂-C₆alkynyl, C(═O)H, C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl), C(═O)(C₃-C₆cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, C₁-C₆alkylphenyl, C₁-C₆ alkyl-O-phenyl, C(═O)Het-1, Het-1, C₁-C₆ alkylHet-1,or C₁-C₆ alkyl-O-Het-1,

-   -   wherein each alkyl, cycloalkyl, alkenyl, alkynyl, phenyl, and        Het-1 are optionally substituted with one or more substituents        independently selected from F, Cl, Br, I, CN, NO₂, NR_(x)R_(y),        C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆ cycloalkyl, C₃-C₆        halocycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy, C₁-C₆        alkoxy, C₁-C₆ haloalkoxy, C₂-C₆ alkenyl, C₃-C₆ cycloalkenyl,        C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl), S(═O)_(n)(C₁-C₆        haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl), C(═O)H,        C(═O)NR_(x)R_(y), (C₁-C₆ alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl),        C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆        haloalkyl), C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl),        C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆ alkenyl), (C₁-C₆        alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆        alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, phenoxy, and Het-1;

(h) R5 is a 2 to 4 membered saturated or unsaturated hydrocarbyl linkagewhere said linkage may also be substituted with at least one OH andoptionally one or more substituents selected from F, Cl, Br, I, CN, NO₂,oxo, NR_(x)R_(y), C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆ cycloalkyl, C₃-C₆halocycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy, C₁-C₆ alkoxy,C₁-C₆ haloalkoxy, C₂-C₆ alkenyl, C₃-C₆ cycloalkenyl, C₂-C₆ alkynyl,S(═O)_(n)(C₁-C₆ alkyl), S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl),OSO₂(C₁-C₆ haloalkyl), C(═O)H, C(═O)OH, C(═O)NR_(x)R_(y), (C₁-C₆alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆ cycloalkyl),C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆ alkenyl),(C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆alkyl)C(═O)O(C₁-C₆ alkyl), phenyl, phenoxy, and Het-1,

-   -   wherein each alkyl, cycloalkyl, cycloalkoxy, alkoxy, alkenyl,        alkynyl, phenyl, phenoxy, and Het-1, are optionally substituted        with one or more substituents independently selected from F, Cl,        Br, I, CN, NO₂, oxo, NR_(x)R_(y), C₁-C₆ alkyl, C₁-C₆ haloalkyl,        C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆        halocycloalkoxy, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆ alkenyl,        C₃-C₆ cycloalkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl),        S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆        haloalkyl), C(═O)H, C(═O)OH, C(═O)NR_(x)R_(y), (C₁-C₆        alkyl)NR_(x)R_(y), C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl),        C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆        cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),        C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆        alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl),        phenyl, halophenyl, phenoxy, and Het-1;

(i) n=0, 1, or 2;

(j) R_(x) and R_(y) are independently selected from H, C₁-C₆ alkyl,C₁-C₆ haloalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₂-C₆ alkenyl,C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl), S(═O)_(n)(C₁-C₆ haloalkyl),OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆ haloalkyl), C(═O)H, C(═O)(C₁-C₆ alkyl),C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆ haloalkyl),C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl),C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), and phenyl,

-   -   wherein each alkyl, cycloalkyl, cycloalkoxy, alkoxy, alkenyl,        alkynyl, phenyl, phenoxy, and Het-1, are optionally substituted        with one or more substituents independently selected from F, Cl,        Br, I, CN, NO₂, oxo, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆        cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆        halocycloalkoxy, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆ alkenyl,        C₃-C₆ cycloalkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl),        S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆        haloalkyl), C(═O)H, C(═O)OH, C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆        alkyl), C(═O)(C₁-C₆ haloalkyl), C(═O)O(C₁-C₆ haloalkyl),        C(═O)(C₃-C₆ cycloalkyl), C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆        alkenyl), C(═O)O(C₂-C₆ alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl),        (C₁-C₆ alkyl)S(C₁-C₆ alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆        alkyl), phenyl, halophenyl, phenoxy, and Het-1,    -   or R_(x) and R_(y) together can optionally form a 5- to        7-membered saturated or unsaturated cyclic group which may        contain one or more heteroatoms selected from nitrogen, sulfur,        and oxygen, and where said cyclic group can contain >C═O        or >C═S, and where said cyclic group may be substituted with F,        Cl, Br, I, CN, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆ cycloalkyl,        C₃-C₆ halocycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy,        C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₂-C₆ alkenyl, C₃-C₆        cycloalkenyl, C₂-C₆ alkynyl, S(═O)_(n)(C₁-C₆ alkyl),        S(═O)_(n)(C₁-C₆ haloalkyl), OSO₂(C₁-C₆ alkyl), OSO₂(C₁-C₆        haloalkyl), C(═O)(C₁-C₆ alkyl), C(═O)O(C₁-C₆ alkyl), C(═O)(C₁-C₆        haloalkyl), C(═O)O(C₁-C₆ haloalkyl), C(═O)(C₃-C₆ cycloalkyl),        C(═O)O(C₃-C₆ cycloalkyl), C(═O)(C₂-C₆ alkenyl), C(═O)O(C₂-C₆        alkenyl), (C₁-C₆ alkyl)O(C₁-C₆ alkyl), (C₁-C₆ alkyl)S(C₁-C₆        alkyl), C(═O)(C₁-C₆ alkyl)C(═O)O(C₁-C₆ alkyl), phenyl,        substituted phenyl, phenoxy, and Het-1; and

(k) Het-1 is a 5- or 6-membered, saturated or unsaturated, heterocyclicring, containing one or more heteroatoms independently selected fromnitrogen, sulfur or oxygen.

It is understood that in Formula 1, when R2 is H, the compounds mayexist in more than one tautomeric or isomeric form, wherein the hydrogenis attached to either of the nitrogen atoms; further, both E and Zisomers may exist. Any and all isomeric forms of the compounds of thisinvention are claimed.

In another embodiment Ar₁ is a substituted phenyl, wherein saidsubstituted phenyl has one or more substituents independently selectedfrom C₁-C₆ haloalkyl and C₁-C₆ haloalkoxy.

In another embodiment Ar₁ is a substituted phenyl, wherein saidsubstituted phenyl has one or more substituents independently selectedfrom CF₃, OCF₃, and OCF₂CF₃.

In another embodiment Het is selected from triazolyl, imidazolyl, orpyrazolyl, which can be substituted or unsubstituted.

In another embodiment Het is a 1,2,4-triazolyl

In another embodiment Het is 1,4-imidazolyl

In another embodiment Het is 1,3-pyrazolyl

In another embodiment Het is a substituted 1,3-pyrazolyl.

In another embodiment Het is 1,4-pyrazolyl

In another embodiment Ar₂ is a phenyl.

In another embodiment R1 is H or C₁-C₆ alkyl.

In another embodiment R1 is H or CH₃.

In another embodiment R2 is H.

In another embodiment R3 is selected from C₁-C₆ alkyl, C₂-C₆ alkenyl,C₂-C₆ alkynyl, C₁-C₆ alkylphenyl, C₁-C₆ alkylHet-1, C₁-C₆alkyl-O—C(═O)C₁-C₆ alkyl-O—C₁-C₆ alkyl, C₁-C₆ alkyl-O—C(═O)C₁-C₆alkyl-O—C₁-C₆ alkyl-O—C₁-C₆ alkyl, C₁-C₆ alkyl-O—C(═O)C₁-C₆alkyl-O—C₁-C₆ haloalkyl, C₁-C₆ alkyl-O—C(═O)C₁-C₆alkyl-N(R_(x))C(═O)—O-phenyl, C₁-C₆ alkyl-O—C(═O)C₁-C₆alkyl-N(R_(x))C(═O)—O—C₁-C₆ alkylphenyl, C₁-C₆ alkylC(═O)N(R_(x))C₁-C₆alkyl, C₁-C₆ alkylC(═O)N(R_(x))C₁-C₆ alkylHet-1C(═O)—O—C₁-C₆ alkyl,C₁-C₆ alkylC(═O)N(R_(x))C₁-C₆ alkylHet-1, C₁-C₆ alkylC(═O)Het-1, C₁-C₆alkylC(═O)N(R_(x))C₁-C₆ alkyl(N(R_(x))(R_(y)))(C(═O)OH), C₁-C₆alkylC(═O)N(R_(x))C₁-C₆ alkylN(R_(x))(R_(y)), C₁-C₆alkylC(═O)N(R_(x))C₁-C₆ alkylN(R_(x))C(═O)—O—C₁-C₆ alkyl, C₁-C₆alkylC(═O)N(R_(x))C₁-C₆ alkyl(N(R_(x))C(═O)—O—C₁-C₆ alkyl)(C(═O)OH),C₁-C₆ alkylC(═O)Het-1C(═O)—O—C₁-C₆ alkyl, C₁-C₆ alkyl-O—C(═O)—O—C₁-C₆alkyl, C₁-C₆ alkyl-O—C(═O)C₁-C₆ alkyl, C₁-C₆ alkyl-O—C(═O)C₃-C₆cycloalkyl, C₁-C₆ alkyl-O—C(═O)Het-1, or C₁-C₆ alkyl-O—C(═O)C₁-C₆alkyl-N(R_(x))C(═O)—O—C₁-C₆ alkyl, wherein each alkyl, alkenyl, alkynyl,phenyl, and Het-1 are optionally substituted with one or moresubstituents independently selected from F, Cl, Br, C₁-C₆ alkyl, C₁-C₆haloalkyl, C₁-C₆ haloalkoxy, S(═O)_(n)(C₁-C₆ alkyl), C(═O)OH,C(═O)O(C₁-C₆ alkyl), phenyl, Si(C₁-C₆ alkyl)₃, and S(═O)_(n)NR_(x)R_(y).

In another embodiment R₄ is phenyl, C₁-C₆ alkylphenyl, Het-1, or C₁-C₆alkyl-O-phenyl, wherein each alkyl, Het-1, and phenyl are optionallysubstituted with one or more substituents independently selected from F,Cl, NR_(x)R_(y), C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₁-C₆ haloalkoxy, C(═O)OC₁-C₆ alkyl, or C₁-C₆ alkoxy.

In another embodiment R5 is substituted with oxo, C(═O)OH, phenyl, andHet-1, wherein each phenyl and Het-1, may be optionally substituted withone or more substituents independently selected from oxo, C₁-C₆haloalkyl, C₁-C₆ haloalkoxy, C(═O)OH, and halophenyl.

In another embodiment R_(x) and R_(y) are independently selected from Hand phenyl, wherein said phenyl, may be optionally substituted with oneor more substituents independently selected from F and Cl.

In another embodiment:

-   -   Ar₁ is a substituted phenyl wherein said substituted phenyl, has        one or more C₁-C₆ haloalkoxy;    -   Het is a triazolyl;    -   Ar₂ is a phenyl;    -   R1 is H;    -   R2 is H;    -   R3 is C₁-C₆ alkylHet-1 wherein said alkyl and Het-1 are        optionally substituted with one or more substituents        independently selected from F, Cl, Br, C₁-C₆ alkyl, C₁-C₆        haloalkyl, C₁-C₆ haloalkoxy, S(═O)_(n)(C₁-C₆ alkyl), C(═O)OH,        C(═O)O(C₁-C₆ alkyl), phenyl, Si(C₁-C₆ alkyl)₃, and        S(═O)_(n)NR_(x)R_(y);    -   R₄ is phenyl, wherein said phenyl is optionally substituted with        one or more substituents independently selected from F, Cl,        NR_(x)R_(y), C₁-C₆ alkyl, or C₁-C₆ alkoxy; and    -   n=0, 1, or 2;    -   R_(x) and R_(y) are independently selected from H and phenyl,        wherein said phenyl, may be optionally substituted with one or        more substituents independently selected from F and Cl; and    -   Het-1 is a 5- or 6-membered, saturated or unsaturated,        heterocyclic ring, containing one or more heteroatoms        independently selected from nitrogen, sulfur or oxygen.

In another embodiment Het-1 is selected from benzofuranyl,benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, benzothienyl,benzothiazolyl cinnolinyl, furanyl, indazolyl, indolyl, imidazolyl,isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, oxadiazolyl,oxazolinyl, oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl, pyrazolyl,pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl,quinoxalinyl, tetrazolyl, thiazolinyl, thiazolyl, thienyl, triazinyl,triazolyl, piperazinyl, piperidinyl, morpholinyl, pyrrolidinyl,tetrahydrofuranyl, tetrahydropyranyl, 1,2,3,4-tetrahydro-quinolinyl,4,5-dihydro-oxazolyl, 4,5-dihydro-1H-pyrazolyl, 4,5-dihydro-isoxazolyl,and 2,3-dihydro-[1,3,4]-oxadiazolyl.

In another embodiment Het is selected benzofuranyl, benzoisothiazolyl,benzoisoxazolyl, benzoxazolyl, benzothienyl, benzothiazolyl cinnolinyl,furanyl, indazolyl, indolyl, imidazolyl, isoindolyl, isoquinolinyl,isothiazolyl, isoxazolyl, oxadiazolyl, oxazolinyl, oxazolyl,phthalazinyl, pyrazinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridyl,pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl, quinoxalinyl,tetrazolyl, thiazolinyl, thiazolyl, thienyl, triazinyl, triazolyl,piperazinyl, piperidinyl, morpholinyl, pyrrolidinyl, tetrahydrofuranyl,tetrahydropyranyl, 1,2,3,4-tetrahydro-quinolinyl, 4,5-dihydro-oxazolyl,4,5-dihydro-1H-pyrazolyl, 4,5-dihydro-isoxazolyl, and2,3-dihydro-[1,3,4]-oxadiazolyl.

In another embodiment Het-1 is selected from benzofuranyl,benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, benzothienyl,benzothiazolyl, benzothiadizolyl, cinnolinyl, furanyl, indazolyl,indolyl, imidazolyl, isoindolyl, isoquinolinyl, isothiazolyl,isoxazolyl, oxadiazolyl, oxazolinyl, oxazolyl, phthalazinyl, pyrazinyl,pyrazolinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl,quinazolinyl, quinolinyl, quinoxalinyl, tetrazolyl, thiazolinyl,thiazolyl, thienyl, thienylpyrazolyl, triazinyl, triazolyl, piperazinyl,piperidinyl, morpholinyl, pyrrolidinyl, tetrahydrofuranyl,tetrahydropyranyl, 1,2,3,4-tetrahydro-quinolinyl, 4,5-dihydro-oxazolyl,4,5-dihydro-1H-pyrazolyl, 4,5-dihydro-isoxazolyl, and2,3-dihydro-[1,3,4]-oxadiazolyl.

In another embodiment Het-1 is selected from benzothiadizolyl, furanyl,oxazolyl, and thienylpyrazolyl.

While these embodiments have been expressed, other embodiments andcombinations of these expressed embodiments and other embodiments arepossible.

The Molecules of Formulae One, Two and Three will generally have amolecular mass of about 100 Daltons to about 1200 Daltons. However, itis generally preferred if the molecular mass is from about 120 Daltonsto about 900 Daltons, and it is even more generally preferred if themolecular mass is from about 400 Daltons to about 800 Daltons.

Preparation of Triaryl-Intermediates

Compounds of this invention can be prepared by making a triarylintermediate, Ar₁-Het-Ar₂, and then linking it to the desiredintermediate to form the desired compound. A wide variety of triarylintermediates can be used to prepare compounds of this invention,provided that such triaryl intermediates contain a suitable functionalgroup on Ar₂ to which the rest of the desired intermediate can beattached. Suitable functional groups include an oxoalkyl or a formylgroup. These triaryl intermediates can be prepared by methods previouslydescribed in the chemical literature, including Crouse et al. PCT Int.Appl. Publ. WO2009/102736 A1.

Preparation of Hydrazone-Linked Compounds

Hydrazone-linked compounds can be prepared from the corresponding arylaldehydes or ketones by one of three methods: (1) by reaction with ahydrazine, followed by reaction with an aryl isothiocyanate intetrahydrofuran (THF), at temperatures between 0 and 100° C. (ReactionA); (2) by reaction with methyl hydrazinecarbodithioate, followed byreaction with an aniline in a polar aprotic solvent such asN,N-dimethylformamide (DMF), at temperatures between 25 and 150° C.(Reaction B); or (3) by reaction with an aryl thiosemicarbazide, that iseither commercially available or can be prepared by one who is skilledin the art, in a polar protic solvent such as ethyl alcohol (EtOH), attemperatures between 0 and 100° C. (Reaction C).

Preparation of Alkylated Hydrazone-Linked Compounds

Alkylated hydrazone-linked compounds can be prepared from thecorresponding hydrazone-linked compounds by one of two methods: (1) byreaction with an alkylating agent in EtOH or acetone, at temperaturesbetween 0 and 100° C. for from 1 to 24 h or (2) by reaction with analkylating agent in chloroform (CHCl₃), dichloromethane (CH₂Cl₂), orother halocarbon solvent, with or without a base such as sodiumbicarbonate, at from 20 to 60° C.

Compounds of Formula Two, wherein R5 forms a ring with N₃ (see Schemebelow) or of Formula Three, wherein R5 forms a ring with N₂, can beprepared from a suitable acyclic precursor by using α-halo acids, acidhalides, esters, or ketones (F or G or H). For example, treatment of thethiosemicarbazone with a slight excess of an α-halo ester, in a proticsolvent such as EtOH or methyl alcohol (CH₃OH) results in S-alkylationand subsequent ring closure exclusively onto N₃ (Reaction F; see forexample, J. Indian Chemical Society 1966, 43, 275-276, or J. Heterocycl.Chem. 1978, 15, 335-336). When an aprotic solvent such as CH₂Cl₂ ordichloroethane (ClCH₂CH₂Cl) is used at temperatures from 30° C. to 80°C., the orientation of addition of α-halo ketones also favors closureonto N₃, with subsequent dehydration to form an imino thiazole (ReactionG). With α-halo acids or acid halides or esters in a halocarbon solventsuch as CH₂Cl₂ or ClCH₂CH₂Cl, ring closure onto both N₂ (Reaction H) andN₃ is observed. Though these reactions often proceed in the absence ofadded base, a base such as sodium bicarbonate, sodium carbonate orsodium acetate, or an amine base such as pyridine or triethylamine, canbe added.

Alternatively, 3-arylidineimino-2-aryliminothiazolin-4-ones can beprepared by treating an aldehyde or ketone, wherein R1 is as previouslydescribed, with a 3-amino-2-(arylimino)thiazolidin-4-one in acetic acidat from 30 to 70° C. as shown in the following scheme (I). Theintermediate 1-amino-2-aryliminothiazolin-5-one, wherein R4 is phenyl,has been described (see for example, J. Org. Chem. 1962, 27, 2878); itwas prepared in 80% yield by treatment of 4-phenyl thiosemicarbazidewith ethyl 2-chloroacetate and sodium acetate in hot EtOH.

Alternatively, compounds of Formula 2 and Formula 3 may be formed byheating a thiosemicarbazone precursor with a di-halo group Hal1-R5-Hal2such as 1-bromo-2-chloro ethane, in acetone or 2-butanone or othersuitable solvent, using a base such as potassium carbonate ortriethylamine, at temperatures between ambient and 100° C. for from 1 to72 hours. The S-alkylated intermediate undergoes cyclization at N2 or N3to generate compounds of Formula Two or Formula Three (Reaction J). Insome cases, addition of KI may be required to accelerate the cyclizationof the intermediate S-alkylated derivatives to the ring-closed products.

An alternative method of preparing compounds of this invention is bytreatment of a thiosemicarbazone precursor with an unsaturated ester oracid chloride (Reaction L).

Compounds of Formula Two, wherein R5 forms a hydroxyl-containing ringwith N₃, or of Formula Three, wherein R5 forms a hydroxyl-containingring with N₂ (see Scheme below), can be prepared from a suitable acyclicprecursor by using an α-halo ketone (Reaction M). This procedure issimilar to Reaction G; under milder conditions (usually ambienttemperature to 90° C.), the intermediate hydroxy thiazoline can beisolated prior to dehydration. This procedure is conveniently conductedin an aprotic solvent such as acetone, 2-butanone or dichloroethane,with or without a base such as triethylamine or sodium bicarbonate. Thedirection of cyclization often favors reaction at N₃, although whenhighly hindered R₄ groups are used, products resulting from cyclizationat N₂ may be formed.

Substituted hydrazinecarbothioamide intermediates, such as thoseutilized in Method C above, can be prepared by a number methods known inthe chemical literature. Alternatively, compounds wherein R_(a), R_(b),and R_(c) are not derived from a commercially available aniline can beprepared according to the scheme below. For example, a 2-halonitrobenzene, such as 2-chloronitrobenzene, substituted with one ormultiple R_(c) substituents, wherein R_(c) can be H, alkyl, alkoxy, orhalo, such as fluoro, can be reacted with a boronic acid or boronateester, such as the substituted 4,4,5,5-tetramethyl-1,3,2-dioxaborolane,wherein R_(a) and R_(b) are H, in the presence of a base, for examplesodium carbonate, and a palladium catalyst, such asbis(triphenylphosphine)palladium(II)chloride, in an aqueous solventsystem, such as 4:1 dioxane/water, at an elevated temperature, forexample 80° C., affords the alkenyl substituted nitrobenzene compounds.Alternatively, R_(a) and R_(b) can be taken together to form a ring,such as a cyclopentene, to give the corresponding2-(cyclopent-1-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, whichunder the conditions described above affords the cyclic alkenesubstituted nitrobenzene. Treatment of a solution of the olefinicnitrobenzenes in an aprotic solvent, such as ethyl acetate, whereinR_(a), R_(b), and R_(c) are as defined above, with hydrogen gas in thepresence of a catalyst, for example palladium on carbon (Pd/C), affordsthe corresponding alkyl or cycloalkyl substituted anilines. Treating abiphasic solution of the anilines, wherein R_(a), R_(b), and R_(c) areas defined, in a mixture of halogenated solvent and water, such as 2:1dichloromethane/water, with a base, such as sodium hydrogencarbonate,followed by thiophosgene affords the intermediateisothiocyanatobenzenes. Separation and removal of the aqueous phase,followed by drying and evaporation of the organic solvent affords thecrude intermediate, which is immediately dissolved in an alcohol, suchas ethanol, and treated with hydrazine hydrate to give thehydrazinecarbothioamide intermediates, wherein R_(a), R_(b), and R_(c)are as defined.

EXAMPLES

The examples are for illustration purposes and are not to be construedas limiting the invention disclosed in this document to only theembodiments disclosed in these examples.

Starting materials, reagents, and solvents that were obtained fromcommercial sources were used without further purification. Anhydroussolvents were purchased as Sure/Seal™ from Aldrich and were used asreceived. Melting points were obtained on a Thomas Hoover Unimeltcapillary melting point apparatus or an OptiMelt Automated Melting PointSystem from Stanford Research Systems and are uncorrected. Molecules aregiven their known names, named according to naming programs within MDLISIS™/Draw 2.5, ChemBioDraw Ultra 12.0 or ACD Name Pro. If such programsare unable to name a molecule, the molecule is named using conventionalnaming rules. ¹H NMR spectral data are in ppm (δ) and were recorded at300, 400 or 600 MHz, and ¹³C NMR spectral data are in ppm (δ) and wererecorded at 75, 100 or 150 MHz, unless otherwise stated.

Example 1 Preparation of(E)-N-(4-dimethylamino)phenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide(Compound I-1) [Synthesis Method A]

Step 1.(E)-3-(4-(Hydrazonomethyl)phenyl)-1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazole

To a 250 milliliter (mL) round-bottomed flask containing hydrazinehydrate (64% aqueous (aq) solution; 7.27 mL, 15.0 millimoles (mmol)) inEtOH (100 mL) at 80° C. was added4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]-benzaldehyde(5.00 grams (g), 1.50 mmol) portionwise over 5 minutes (min) Thesolution was stirred at reflux for an additional 3 hours (h) beforebeing diluted with water (H₂O; 300 mL) and cooled to 0° C. Theprecipitated product was collected by vacuum filtration as a white solid(4.89 g, 93%): mp 222-226° C.; ¹H NMR (400 MHz, DMSO-d₆) δ 8.59 (s, 1H),8.22 (d, J=8.2 Hz, 2H), 7.84-7.79 (m, 3H), 7.66 (d, J=8.3 Hz, 2H), 7.41(d, J=8.2 Hz, 2H), 7.29 (s, 1H), 5.63 (br s, 2H); ESIMS m/z 348 (M+H).

Step 2

To a 25 mL round-bottomed flask containing(E)-3-(4-(hydrazonomethyl)-phenyl)-1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazole(250 mg, 0.720 mmol) in THF (10 mL) was added4-isothiocyanato-N,N-dimethylaniline (385 mg, 2.16 mmol). The contentswere heated at 65° C. with stirring for 2 h before the solvent wasremoved under reduced pressure. The residue was slurried in CH₂Cl₂ (10mL) resulting in precipitation of product material. The desired productwas obtained as a yellow solid via vacuum filtration (350 mg, 93%): mp205-208° C.; ¹H NMR (400 MHz, DMSO-d₆) δ 11.78 (s, 1H), 10.02 (s, 1H),9.42 (s, 1H), 8.19-7.99 (m, 6H), 7.64 (d, J=8.3 Hz, 2H), 7.28 (d, J=8.3Hz, 2H), 7.73 (d, J=8.3 Hz, 2H), 2.92 (s, 6H); ESIMS m/z 526 (M+H).

Example 2 Preparation ofN-(3-(dimethylamino)phenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide(Compound I-2) [Synthesis Method B]

Step 1. (E)-Methyl2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbodithioate

To a 250 mL round-bottom flask containing hydrazinecarbodithioic acidmethyl ester (2.38 g, 1.95 mmol) in EtOH (100 mL) was added4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]-benzaldehyde(5.00 g, 1.50 mmol). The vessel was heated at 80° C. for 3 h beforebeing diluted with H₂O (300 mL) and cooled to 0° C. The precipitatedproduct was collected by vacuum filtration as an off-white solid (6.13g, 93%): mp 204-206° C.; ¹H NMR (400 MHz, DMSO-d₆) δ 13.39 (s, 1H), 9.43(s, 1H), 8.38 (s, 1H), 8.21 (d, J=8.3 Hz, 2H), 8.09 (d, J=8.4 Hz, 2H),7.88 (d, J=8.4 Hz, 2H), 7.62 (d, J=8.3 Hz, 2H), 2.57 (s, 3H); ESIMS m/z438 (M+H).

Step 2

To a 50 mL round-bottomed flask containing (E)-methyl2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbodithioate(250 mg, 0.571 mmol) in DMF (3 mL) was addedN1,N1-dimethylbenzene-1,3-diamine (195 mg, 1.43 mmol). The contents wereheated at 150° C. with stirring for 5 h before the solution was allowedto cool overnight. The mixture was filtered, and the filtrate waspurified via RP-HPLC to afford the desired material (235 mg, 78%) as anoff-white solid: mp 192-194° C.; ¹H NMR (400 MHz, DMSO-d₆) δ 11.82 (s,1H), 10.04 (s, 1H), 9.41 (s, 1H), 8.19 (s, 1H), 8.16-7.99 (m, 6H), 7.61(d, J=8.3 Hz, 2H), 7.16 (t, J=7.2 Hz, 1H), 7.01 (m, 1H), 6.87 (m, 1H),6.58 (m, 1H), 2.88 (s, 6H); ESIMS m/z 526 ([M+1-1]⁺).

Example 3 Preparation ofN-benzyl-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide(Compound I-3) [Synthesis Method C]

To a 50 mL round-bottomed flask containing4-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]benzaldehyde (500mg, 1.5 mmol) in EtOH (3 mL) was added 4-benzylthiosemicarbazide (650mg, 3.6 mmol). The reaction mixture was heated at 80° C. overnight. H₂Owas added upon completion of the reaction, and the crude productmaterial was isolated by vacuum filtration. The title compound wasisolated via RP-HPLC as a white solid (390 mg, 52%): mp 220-224° C.; ¹HNMR (400 MHz, CDCl₃) δ 9.29 (s, 1H), 8.59 (s, 1H), 8.21 (d, J=8.4 Hz,2H), 7.85-7.79 (m, 3H), 7.71 (d, J=8.4 Hz, 2H), 7.46-7.30 (m, 8H), 5.01(d, J=5.8 Hz, 2H); ESIMS m/z 497.2 (M+H).

Compounds I-4 through I-31 in Table 1 were synthesized in accordancewith the examples above. Other intermediates used in the preparation ofcompounds of this invention were prepared in accordance with theprocedures described in Brown, et al, WO 2011017504 A1, or by otherknown routes.

Example 4 Preparation ofN-(4-dimethylaminophenyl)-S-methyl-2-{4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]-triazol-3-yl]-benzylidene}-hydrazine-carbothioamide(Compound 1C) (Synthesis Method D)

A solution containing(E)-N-(4-(dimethylamino)phenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide(150 mg, 0.285 mmol) and iodomethane (0.054 mL, 0.856 mmol) in EtOH (5mL) was heated at 80° C. for 3 h before the solvent was removed underreduced pressure. The residue was purified via normal phase flashchromatography (gradient elution with hexanes/EtOAc) to afford the titlecompound as an orange foam (93 milligrams (mg), 60%): ¹H NMR (400 MHz,DMSO-d₆) δ 8.61 (s, 1H), 8.48 (s, 1H), 8.22 (d, J=8.24 Hz, 2H), 8.17 (s,1H), 7.89 (d, J=8.24 Hz, 2H), 7.80 (d, J=8.28 Hz, 2H), 7.41 (d, J=8.28Hz, 2H), 7.19 (d, J=8.24 Hz, 2H), 6.71 (d, J=8.24 Hz, 2H), 2.99 (s, 6H),2.42 (s, 3H); EIMS m/z 540 (M⁺).

Example 5 General Procedure for S-Alkylation of TriarylThiosemicarbazones (Synthesis Method E)

A stirred solution of the thiosemicarbazone and alkylating reagent inCH₂Cl₂ or chloroform (CHCl₃) was heated at from 35 to 50° C. for from 10to 24 h. The cooled solution was concentrated under reduced pressure.The residue was generally purified via chromatography using achloroform/methanol (CHCl₃/CH₃OH) or EtOAc-hexane solution as the eluentto afford the S-alkylated products.

Example 6 Preparation of (S)-tert-butyl3-((2-((Z)-(2,6-dimethylphenylimino)-((E)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinyl)-methylthio)acetamido)methyl)piperidine-1-carboxylate(Compound 56C) (Synthesis Method E)

To a solution of bromoacetyl bromide (26 microliters (μL), 0.299 mmol)in dichloroethane (3 mL) was added dropwise a solution of (S)-tert-butyl3-(aminomethyl)piperidine-1-carboxylate (63.9 mg, 0.298 mmol) indichloromethane (1 mL), followed by N-ethyl-N-isopropylpropan-2-amine(76 mg, 0.588 mmol). This mixture was stirred at room temperature for 30min, then(E)-N-(2,6-dimethylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazine-carbothioamide(100 mg, 0.196 mmol) was added as a solid and the mixture was heated to40° C. for 90 min. It was then allowed to cool to room temperature andevaporated under reduced pressure, giving a light yellow glass, whichwas dissolved in acetonitrile (2 mL) and allowed to stand at roomtemperature. The resulting precipitate was isolated by centrifuge anddecanting, washing with fresh acetonitrile. The solid was dried under anitrogen stream and then under high vacuum. The crude product wasrecrystallized from acetone-isopropyl alcohol. The title compound wasisolated as a white solid (36.5 mg, 24%): mp 148-151° C.; ¹H NMR (400MHz, methanol-d₄) δ 9.18 (s, 1H), 8.59 (s, 1H), 8.30 (d, J=8.1 Hz, 2H),8.12 (m, 2H), 8.07-8.00 (m, 2H), 7.58-7.43 (m, 2H), 7.33 (dd, J=8.6, 6.5Hz, 1H), 7.25 (d, J=7.6 Hz, 2H), 4.02 (m, 2H), 3.97-3.75 (m, 2H), 3.21(d, J=6.9 Hz, 2H), 2.90 (m, 1H), 2.59 (m, 1H), 2.35 (s, 6H), 1.84 (m,2H), 1.78-1.63 (m, 2H), 1.44 (s, 9H), 1.29 (m, 3H); ESIMS m/z 765 (M+H).

Example 7 Preparation of(1Z,2E)-2-oxo-2-(((R)-piperidin-3-ylmethyl)amino)ethylN-(2,6-dimethylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbimidothioatetrifluoroacetic acid (Compound 62C) (Synthesis Method K)

A solution of (S)-tert-butyl3-((2-((Z)-(2,6-dimethylphenylimino)-((E)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinyl)methylthio)-acetamido)methyl)piperidine-1-carboxylate(32.0 mg, 0.042 mmol) in TFA (250 μL, 3.24 mmol) was stirred at roomtemperature for 10 min. Et₂O (10 mL) was then added giving a whiteprecipitate, which was isolated by centrifuge and decanting, thenrinsing with fresh Et₂O (5 mL). The solid was dried under nitrogenstream and then under high vacuum giving the title compound as a whitesolid (19.8 mg, 60%): mp 110-120° C.; ¹H NMR (400 MHz, methanol-d₄) δ9.18 (s, 1H), 8.56 (m, 1H), 8.26 (m, 2H), 8.16-7.84 (m, 4H), 7.52 (m,2H), 7.27 (m, 1H), 7.22 (m, 2H), 4.00 (s, 2H), 3.28 (m, 3H), 3.06-2.83(m, 1H), 2.75 (t, J=12.2 Hz, 1H), 2.34 (s, 6H), 2.21-1.83 (m, 4H), 1.72(m, 1H), 1.47-1.19 (m, 2H); ESIMS m/z 665 (M+H).

Example 8 Preparation of2-(((Z)-((4-methoxy-2,6-dimethylphenyl)imino)((E)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinyl)methyl)-thio)aceticacid sodium salt (Compound 68C)

To a solution of2-((Z)-(4-methoxy-2,6-dimethylphenylimino)((E)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinyl)methylthio)aceticacid (77.7 mg, 0.130 mmol) in THF (10 mL) was added slowly sodiummethanolate (0.5 M in methanol; 260 μL, 0.130 mmol) at room temperature.The mixture immediately turned a darker yellow and was then evaporatedat room temperature under vacuum giving a light orange solid. Thismaterial was triturated with Et₂O (2×) and isolated by decanting using acentrifuge and drying under a nitrogen stream and then under highvacuum. The title compound was isolated as a light orange solid (32 mg,39%): mp 146-154° C.; ¹H NMR (400 MHz, methanol-d₄) δ 9.11 (s, 1H),8.64-7.68 (m, 7H), 7.51 (m, 2H), 6.70 (s, 2H), 3.85-3.70 (m, 4H), 3.61(m, 1H), 2.29 (s, 6H); ESIMS m/z 599 (M+H).

Example 9 Preparation of(Z)-3-(4-methoxy-2,6-dimethylphenyl)-2-((E)-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)thiazolidin-4-one(Compound 69C) (Synthesis Method F)

To a solution of(E)-N-(4-methoxy-2,6-dimethylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazine-carbothioamide(250 mg, 0.462 mmol) in EtOH (5 mL) was added methyl bromoacetate (100mg, 0.65 mmol), and the mixture was heated to 70° C. for 4 h. Themixture was allowed to cool to room temperature and diluted with water(1 mL). The precipitate was vacuum filtered, giving the title compoundas a white solid (204 mg, 76%): mp 188-190° C.; ¹H NMR (400 MHz, CDCl₃)δ 8.56 (s, 1H), 8.33 (s, 1H), 8.22 (d, J=8.1 Hz, 2H), 7.90-7.70 (m, 4H),7.39 (d, J=8.7 Hz, 2H), 6.72 (s, 2H), 4.01 (s, 2H), 3.87-3.73 (s, 3H),2.18 (s, 6H); ESIMS m/z 581 (M+H).

Example 10 Preparation of4-((2Z)-3-(2,6-dimethylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)-2,3-dihydrothiazol-4-yl)-N,N-diethylaniline(Compound 74C) (Synthesis Method G)

To a solution of(E)-N-(2,6-dimethylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazine-carbothioamide(74.7 mg, 0.144 mmol) in dichloroethane (5 mL), was addedα-bromo-4-diethylamino)acetophenone (53.9 mg, 0.199 mmol), and themixture was heated to 40° C. for 4 h. The mixture was then cooled toroom temperature and evaporated under vacuum. The crude material wastriturated with acetonitrile and decanted (2×). The resulting solid wasdried under a stream of nitrogen, giving the title compound as a paleyellow solid (25 mg, 25%): mp 190-193° C. dec; ¹H NMR (400 MHz,methanol-d₄) δ 9.20 (s, 1H), 8.38 (s, 1H), 8.31-8.24 (m, 2H), 8.08-8.00(m, 2H), 7.95-7.88 (m, 2H), 7.55-7.48 (m, 3H), 7.48-7.36 (m, 5H), 7.31(d, J=7.7 Hz, 2H), 3.60 (q, J=7.2 Hz, 4H), 2.20 (s, 6H), 1.07 (t, J=7.2Hz, 6H); ESIMS m/z 682 (M+H).

Example 11 Preparation of(Z)-2-(2,6-dimethylphenylimino)-3-(E)-4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylideneamino)thiazolidin-4-one(Compound 81C) (Synthesis Method I)

To a solution of 1-(2,6-dimethylphenyl)thiourea (1.0 g, 5.55 mmol) inEtOH (10 mL) was added methyl 2-bromoacetate (1.0 g, 6.5 mmol) andsodium acetate (1.0 g, 12.2 mmol). The solution was stirred and heatedto reflux for 1 h, then it was cooled and the liquid was decanted from asmall amount of solid material and the liquid was then diluted withwater (10 mL). The precipitate was isolated by filtration to give (1.1g, 83%) of (Z)-3-amino-2-(2,6-dimethylphenylimino)thiazolidin-4-one: mp149-152° C.; ¹H NMR (400 MHz, CDCl₃) δ 7.06 (d, J=7.2 Hz, 2H), 6.98 (m,1H), 4.75 (s, 2H), 3.80 (s, 2H), 2.12 (s, 6H); ESIMS m/z 236 (M+H).

A portion of this material (0.07 g, 0.3 mmol) was dissolved in glacialacetic acid (3 mL) and treated with4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzaldehyde(0.10 g, 0.30 mmol), and the solution was heated to 60° C. for 2 h. Thesolution was then cooled and diluted with water (1 mL), and theresulting solid was filtered and air-dried to give the title compound(0.12 g, 67%): mp 209-213° C.; ¹H NMR (400 MHz, CDCl₃) δ 9.42 (s, 1H),8.59 (s, 1H), 8.28 (d, J=8.4 Hz, 2H), 8.01 (d, J=8.3 Hz, 2H), 7.80-7.77(m, 2H), 7.43-7.34 (m, 2H), 7.07 (d, J=7.5 Hz, 2H), 6.98 (dd, J=8.2, 6.7Hz, 1H), 3.90 (s, 2H), 2.17 (s, 6H); ESIMS m/z 551 (M+H).

Example 12 Preparation of(2Z,NE)-2-(2-isopropylphenyl)imino)-N-(4-(1-(4-(trifluoromethyl)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)-1,3-thiazinan-3-amineand(Z)-3-(2-isopropylphenyl)-2-(E)-(4-(1-(4-(trifluoromethyl)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)-1,3-thiazinane(Compound 87C and 179C) (Synthesis Method J)

To(E)-N-(2-isopropylphenyl)-2-(4-(1-(4-(trifluoromethyl)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide(200 mg, 0.393 mmol) and potassium carbonate (217 mg, 1.57 mmol) inbutanone (10 ml) in a 25 mL vial equipped with a stir bar and vigruexcolumn was added 1-bromo-3-chloropropane (0.047 ml, 0.472 mmol). Thereaction was heated to 60° C. overnight. The reaction was determined tobe complete by LCMS. The reaction mixture was diluted with DCM andwashed with water. The aqueous layer was extracted with DCM. The organiclayers were poured through a phase separator and concentrated.Purification by flash column chromatography provided two compounds. Theminor compound was dried overnight under house vacuum providing thetitle compound 87C(2Z,NE)-2-((2-isopropylphenyl)imino)-N-(4-(1-(4-(trifluoromethyl)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)-1,3-thiazinan-3-amine(28.5 mg, 13%) as a yellow solid: mp 187-189° C.; ¹H NMR (400 MHz,CDCl₃) δ 8.81 (s, 1H), 8.66 (s, 1H), 8.21 (d, J=8.3 Hz, 2H), 7.92 (d,J=8.4 Hz, 2H), 7.81 (t, J=10.2 Hz, 4H), 7.30-7.26 (m, 2H), 7.17-7.04 (m,1H), 6.83 (d, J=6.4 Hz, 1H), 3.96 (t, J=6.1 Hz, 2H), 3.13 (heptet, J=6.9Hz, 1H), 2.97-2.90 (m, 2H), 2.47-2.38 (m, 2H), 1.25 (d, J=7.5 Hz, 6H);ESIMS m/z 550 (M+H). The major compound was recrystallized with MeOH.The solid was filtered, washed with MeOH and dried at 50° C. undervacuum. The solid was then azeotroped with acetone (3×) and theresultant solid was dried at 50° C. under vacuum providing the titlecompound 179C(Z)-3-(2-isopropylphenyl)-2-((E)-(4-(1-(4-(trifluoromethyl)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)-1,3-thiazinaneas a yellow solid (92.3 mg, 0.168 mmol, 43%): mp 212-213° C.; ¹H NMR(400 MHz, CDCl₃) δ 8.64 (s, 1H), 8.15 (d, J=8.4 Hz, 2H), 8.06 (s, 1H),7.91 (d, J=8.5 Hz, 2H), 7.79 (d, J=8.6 Hz, 2H), 7.75 (d, J=8.4 Hz, 2H),7.38 (dd, J=7.8, 1.6 Hz, 1H), 7.33 (td, J=7.5, 1.4 Hz, 1H), 7.29-7.23(m, 1H), 7.18 (dd, J=7.8, 1.4 Hz, 1H), 3.78-3.72 (m, 1H), 3.59-3.48 (m,1H), 3.18-3.04 (m, 3H), 2.40-2.30 (m, 2H), 1.26-1.20 (m, 6H); ESIMS m/z550 (M+H).

Example 13 Preparation of(Z)-3-(2-cyclopropylphenyl)-5-methyl-2-((E)-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)thiazolidin-4-one(Compound 127C) (Synthesis Method F)

To(E)-N-(2-cyclopropylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide(100 mg, 0.191 mmol) and sodium acetate (63.0 mg, 0.765 mmol) in EtOH (4mL) was added methyl 2-bromopropanoate (0.026 mL, 0.230 mmol). Thereaction was heated to 60° C. overnight. The reaction was then heated to85° C. for 72 hours. The reaction mixture was diluted with DCM andwashed with water. The aqueous layer was extracted with DCM. The organiclayers were poured through a phase separator and concentrated.Purification by flash column chromatography provided the title compoundas a white solid (32.5 mg, 0.056 mmol, 30%): mp 112-115° C.; ¹H NMR (400MHz, CDCl₃) δ 8.58 (s, 1H), 8.32 (s, 1H), 8.22 (d, J=8.3 Hz, 2H),7.87-7.75 (m, 4H), 7.43-7.32 (m, 4H), 7.26-7.24 (m, 2H), 4.23 (q, J=7.3Hz, 1H), 1.85-1.78 (m, 4H), 0.90-0.78 (m, 2H), 0.78-0.69 (m, 1H),0.65-0.55 (m, 1H); ESIMS m/z 578 (M+H).

Example 14 Preparation of(Z)-3-(2-isopropylphenyl)-2-((E)-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)thiazolidine(Compound 132C) (Synthesis Method J)

To(E)-N-(2-isopropylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide(214 mg, 0.407 mmol) and potassium carbonate (225 mg, 1.63 mmol) inbutanone (4 ml) was added 1-bromo-2-chloroethane (70.0 mg, 0.489 mmol).The reaction was heated to 90° C. overnight. The reaction was determinedto be complete by LCMS. The reaction mixture was cooled, diluted withDCM and washed with water. The aqueous layer was extracted with DCM. Theorganic layers were filtered through a phase separator and concentrated.Separation by flash column chromatography and drying the recovered solidat 55° C. under vacuum provided the title compound as a white solid (137mg, 0.249 mmol, 61%): mp 193-196° C.; ¹H NMR (400 MHz, CDCl₃) δ 8.56 (s,1H), 8.22 (s, 1H), 8.17 (d, J=8.4 Hz, 2H), 7.80 (ddd, J=9.5, 6.9, 4.9Hz, 4H), 7.43-7.33 (m, 4H), 7.31-7.21 (m, 2H), 4.05 (td, J=9.4, 7.1 Hz,1H), 3.97-3.87 (m, 1H), 3.42-3.33 (m, 1H), 3.33-3.24 (m, 1H), 3.12(heptet, J=6.8 Hz, 1H), 1.27 (d, J=6.8 Hz, 3H), 1.22 (d, J=6.9 Hz, 3H);ESIMS m/z 552 (M+H).

Example 15 Preparation of(Z)-3-(2-isopropylphenyl)-4-methyl-2-((E)-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)thiazolidine(Compound 155C) (Synthesis Method J)

To(E)-N-(2-isopropylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide(300 mg, 0.572 mmol) and potassium carbonate (316 mg, 2.29 mmol) inbutanone (4 ml) was added 1,2-dibromopropane (0.072 ml, 0.686 mmol). Thereaction was heated to 85° C. overnight. The reaction was determined tobe complete by LCMS. The reaction mixture was diluted with DCM andwashed with water. The aqueous layer was extracted with DCM. The organiclayers were poured through a phase separator and concentrated.Purification by flash column chromatography provided a yellow solid. Thesolid was recrystallized from MeOH. The solid was filtered, washed withMeOH, and dried to provide the title compound as a yellow solid whichwas dissolved in acetone and concentrated (3×). The light yellow solidwas collected and dried under to provide the title compound as a 1:1mixture of rotational diastereoisomers (75.1 mg, 0.133 mmol, 23%): mp201-204° C.; ¹H NMR of mixture (400 MHz, CDCl₃) δ 8.56 (s, 2H), 8.18(dd, J=10.8, 7.4 Hz, 6H), 7.84-7.73 (m, 8H), 7.45-7.30 (m, 8H),7.30-7.23 (m, 2H), 7.20 (d, J=6.7 Hz, 1H), 7.12 (dd, J=7.8, 1.2 Hz, 1H),4.43-4.33 (m, 1H), 4.16 (dd, J=12.6, 6.3 Hz, 1H), 3.48 (dt, J=13.3, 6.7Hz, 1H), 3.37 (dd, J=10.8, 6.2 Hz, 1H), 3.24 (dt, J=13.7, 6.9 Hz, 1H),3.08-2.92 (m, 3H), 1.33-1.16 (m, 18H); ESIMS m/z 566 (M+H).

Example 16 Preparation of(Z)-3-(2,6-dimethylphenyl)-4-methyl-2-((E)-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)-2,3-dihydrothiazole(Compound 173C) (Synthesis Method G)

To a solution of(E)-N-(o-tolyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide(257 mg, 0.520 mmol) in butanone (5 mL) was added triethylamine (0.14mL, 1.0 mmol) and chloroacetone (0.06 mL, 0.73 mmol) and refluxed at 75°C. for 15 h. The mixture was allowed to cool to room temperature andthen transferred to a separatory funnel containing water (5 mL) andextracted twice with dichloromethane. The organic layers were filteredthrough a phase separator, adsorbed onto silica gel, and purified byflash column chromatography to afford the title compound as a yellowsolid (229 mg, 83%): mp 87° C. (dec); ¹H NMR (400 MHz, CDCl₃) δ 8.56 (s,1H), 8.19-8.15 (m, 3H), 7.82-7.75 (m, 4H), 7.43-7.30 (m, 5H), 7.24 (d,J=7.3 Hz, 1H), 5.88 (d, J=1.3 Hz, 1H), 2.21 (s, 3H), 1.80 (d, J=1.2 Hz,3H); ESIMS m/z 536 (M+H).

Example 17 Preparation of(Z)-3-(2-isopropylphenyl)-5-methyl-2-((E)-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)-1,3-thiazinane(Compound 178C) (Synthesis Method J)

To(E)-N-(2-isopropylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide(100 mg, 0.191 mmol) and potassium carbonate (105 mg, 0.763 mmol) inbutanone (4 ml) was added 1-bromo-3-chloro-2-methylpropane (39.0 mg,0.229 mmol). The reaction was heated to 80° C. overnight. The reactionmixture was then diluted with DCM and washed with water. The aqueouslayer was extracted with DCM. The organic layers were poured through aphase separator and concentrated. Purification by flash columnchromatography provided the title compound as a light yellow solid as amixture of rotational diastereoisomers: mp 186-190° C.; ¹H NMR (400 MHz,CDCl₃) δ 8.55 (d, J=3.6 Hz, 1H), 8.14 (d, J=8.4 Hz, 2H), 8.06 (s, 1H),7.84-7.77 (m, 2H), 7.74 (d, J=8.4 Hz, 2H), 7.38 (d, J=9.0 Hz, 3H), 7.32(td, J=7.5, 1.4 Hz, 1H), 7.26 (s, 1H), 7.17 (t, J=7.1 Hz, 1H), 3.69-3.26(m, 1H), 3.55-3.37 (m, 1H), 3.18-2.98 (m, 2H), 2.93-2.80 (m, 1H), 2.47(d, J=35.9 Hz, 1H), 1.31-1.12 (m, 9H); ESIMS m/z 580 (M+H).

Example 18 Preparation of(Z)-3-(2,6-dimethylphenyl)-2-(E)-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)-1,3-thiazepane(Compound 211C) (Synthesis Method J)

To(E)-N-(2,6-dimethylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide(500 mg, 0.979 mmol) and potassium carbonate (541 mg, 3.92 mmol) inacetone (4 ml) was added 1-bromo-4-chlorobutane (0.135 ml, 1.18 mmol).The reaction was heated to 60° C. overnight. The alkylation wasdetermined to be complete by ultra performance liquid chromatography(“UPLC”). The reaction mixture was diluted with DCM and washed withwater. The aqueous layer was extracted with DCM. The organic layers werepoured through a phase separator and concentrated. Purification by flashcolumn chromatography provided (1Z,N′E)-4-chlorobutylN-(2,6-dimethylphenyl)-N′-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)carbamohydrazonothioate(427 mg, 0.710 mmol, 73%) as a yellow gum which was used without furtherpurification. To (1Z,N′E)-4-chlorobutylN-(2,6-dimethylphenyl)-N′-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)-carbamohydrazonothioate(427 mg, 0.710 mmol), potassium iodide (236 mg, 1.42 mmol) and potassiumcarbonate (393 mg, 2.84 mmol) was added acetone (7 ml). The reaction washeated to 65° C. for 72 h. The reaction was cooled to room temperature,diluted with DCM and washed with water. The aqueous layer was extractedwith DCM. The organic layers were poured through a phase separator andconcentrated. Purification by flash column chromatography provided ayellow oil. The yellow oil was recrystallized from MeOH, filtered,washed with MeOH and dried to provide the title compound as a yellowsolid (100 mg, 0.177 mmol, 25%): mp 100-106° C.; ¹H NMR (400 MHz, CDCl₃)δ 8.55 (s, 1H), 8.15 (d, J=8.4 Hz, 2H), 8.10 (s, 1H), 7.79 (dt, J=10.4,5.8 Hz, 4H), 7.38 (d, J=8.3 Hz, 2H), 7.11 (s, 3H), 3.85-3.78 (m, 2H),3.20-3.12 (m, 2H), 2.30 (s, 6H), 2.13-2.07 (m, 2H), 1.87-1.82 (m, 2H);ESIMS m/z 566 (M+H).

Example 19 Preparation of(Z)-3-(2-isopropylphenyl)-2-((E)-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)-1,3-thiazinan-4-one(Compound 224C) (Synthesis Method L)

To(E)-N-(2-isopropylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide(500 mg, 0.953 mmol) in butanone (9.5 ml) was added acryloyl chloride(0.077 ml, 0.953 mmol). The reaction was stirred at ambient temperaturefor 10 min followed by 50° C. for 2 h. The reaction was cooled to 40° C.overnight. The reaction was determined to be complete by LCMS. Thereaction mixture was diluted with DCM and washed with saturated sodiumbicarbonate. The aqueous layer was extracted with DCM. The organiclayers were poured through a phase separator and concentrated.Purification by flash column chromatography provided a yellow oil. Theoil was recrystallized with diethyl ether/hexanes to provide the titlecompound as a light yellow solid (125 mg, 0.217 mmol, 23%): mp 118° C.(dec); ¹H NMR (400 MHz, CDCl₃) δ 8.57 (s, 1H), 8.21 (d, J=8.4 Hz, 2H),8.16 (s, 1H), 7.85-7.75 (m, 4H), 7.46-7.36 (m, 4H), 7.33-7.26 (m, 1H),7.10 (d, J=7.6 Hz, 1H), 3.26-3.14 (m, 4H), 2.81 (heptet, J=6.9 Hz, 1H),1.21 (t, J=7.2 Hz, 6H); ESIMS m/z 580 (M+H).

Example 20 Separation of Rotationally Stable Atropisomers from RacemicMixtures

Separation of constituent isomers from racemic mixtures can be carriedout utilizing one of the following chiral HPLC methods.

Separation Method A:

The column used for separation was a Chiral Technologies INC Chiral Pak1A 5 μm, 4.6×250 mm column (Part number 80325). The method consists of a1.0 mL/min flow rate from 0 to 30 min with an isocratic hold at 25% Bfor the duration of the run. The A eluent is n-hexane, the B eluent isiso-propyl alcohol.

Separation Method B:

The column used for separation was a Chiral Technologies INC Chiral Pak1B 5 μm, 4.6×250 mm column (Part number 81325). The method consists of a1.0 mL/min flow rate from 0 to 30 min with an isocratic hold at 15% Bfor the duration of the run. The A eluent is n-pentane, the B eluent isn-butyl alcohol.

Example 21 Preparation of(Z)-3-(2,6-difluorophenyl)-4-methyl-2-((E)-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)thiazolidin-4-ol(Compound 240C; Synthesis Method M)

To a solution of(E)-N-(2,6-difluorophenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide(253 mg, 0.49 mmol) in butanone (4.9 mL) was added triethylamine (0.14mL, 0.98 mmol) and chloroacetone (0.055 mL, 0.68 mmol), and the reactionwas stirred at 80° C. for 15 hours. The mixture was allowed to cool toroom temperature, transferred to a separatory funnel containing water (5mL), and extracted twice with dichloromethane. The organic extracts werefiltered through a phase separator, adsorbed onto silica gel, andpurified by flash chromatography (0-20% ethyl acetate/B, where B=1:1dichloromethane/hexanes) to afford the title compound as a yellow solid(248 mg, 88%): mp 105° C. (dec); ¹H NMR (400 MHz, CDCl₃) δ 8.57 (s, 1H),8.25-8.12 (m, 3H), 7.88-7.72 (m, 4H), 7.39 (d, J=8.5 Hz, 3H), 7.06 (td,J=8.9, 4.4 Hz, 2H), 3.58 (d, J=11.5 Hz, 1H), 3.37 (d, J=11.5 Hz, 1H),3.24 (d, J=2.7 Hz, 1H), 1.59 (s, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ −58.02,−113.71, −115.83, −115.84; ESIMS m/z 576 (M+H)⁺.

Example 22 Preparation of(Z)-2-((2-chloro-6-(trifluoromethyl)phenyl)imino)-4-methyl-3-((E)-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)amino)thiazolidin-4-ol(Compound 241C; Synthesis Method M)

To a solution of(E)-N-(2-chloro-6-(trifluoromethyl)phenyl)-2-(4-(1-(4-(trifluoromethoxy)-phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide(111 mg, 0.19 mmol) in butanone (2 mL) was added chloroacetone (0.02 mL,0.27 mmol) and triethylamine (0.05 mL, 0.38 mmol), and the reaction wasstirred at 75° C. for 16 hours. The mixture was allowed to cool to roomtemperature, transferred to a separatory funnel containing water (5 mL),and was extracted twice with dichloromethane. The organic extracts werefiltered through a phase separator, adsorbed onto silica gel, andpurified by flash chromatography (0-20% ethyl acetate/B, where B=1:1dichloromethane/hexanes). The title compound was isolated as a yellowsolid (60.5 mg, 50%): mp 97° C. (dec); ¹H NMR (400 MHz, CDCl₃) δ9.72-9.57 (m, 1H), 8.58 (s, 1H), 8.24 (d, J=8.4 Hz, 2H), 7.88-7.72 (m,4H), 7.56 (dt, J=18.3, 5.8 Hz, 2H), 7.40 (d, J=8.3 Hz, 2H), 7.09 (t,J=8.0 Hz, 1H), 3.49 (d, J=13.3 Hz, 1H), 3.35 (m, 2H), 1.86 (d, J=14.0Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ−58.01, −62.05, −62.22; ESIMS m/z 642(M+H).

Example 23 Preparation of(Z)-3-(2-isopropylphenyl)-4-methyl-2-((E)-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)thiazolidin-4-ol(Compound 242C; Synthesis Method M)

To a solution of(E)-N-(2-isopropylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide(134 mg, 0.26 mmol) in butanone (1.9 mL) was added chloroacetone (0.03mL, 0.33 mmol) and triethylamine (0.04 mL, 0.28 mmol), and the reactionwas stirred at room temperature for 16 hours. The mixture wastransferred to a separatory funnel containing water (5 mL) and extractedtwice with dichloromethane. The organic extracts were filtered through aphase separator, adsorbed onto silica gel, and purified by flashchromatography (0-25% ethyl acetate/B, where B=1:1dichloromethane/hexanes) to provide the title compound as a yellow solid(117 mg, 79%): mp 114-116° C.; ¹H NMR (400 MHz, CDCl₃) δ 8.57 (s, 1H),8.19 (dd, J=10.1, 6.2 Hz, 3H), 7.79 (dd, J=11.5, 4.7 Hz, 4H), 7.50-7.44(m, 1H), 7.44-7.36 (m, 4H), 7.29-7.25 (m, 1H), 3.55 (d, J=11.5 Hz, 1H),3.45 (s, 1H), 3.34 (d, J=11.5 Hz, 1H), 2.98 (dt, J=13.8, 6.9 Hz, 1H),1.43 (s, 3H), 1.27-1.16 (m, 6H); ¹⁹F NMR (376 MHz, CDCl₃) δ −58.02;ESIMS m/z 582 (M+H)⁺.

Example 24 Preparation of(Z)-3-(2-(sec-butyl)phenyl)-4-methyl-2-((E)-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)thiazolidin-4-ol(Compound 243C; Synthesis Method M)

Starting from(E)-N-(2-sec-butylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide,and using conditions described in Example 23, the title compound wasisolated as a yellow solid (122 mg, 89%): mp 112° C. (dec); ¹H NMR (400MHz, CDCl₃) δ 8.57 (s, 1H), 8.23-8.13 (m, 3H), 7.84-7.74 (m, 4H),7.55-7.44 (m, 1H), 7.43-7.32 (m, 4H), 7.28-7.24 (m, 1H), 3.55-3.51 (m,2H), 3.32 (dd, J=11.5, 1.0 Hz, 1H), 2.69 (td, J=13.9, 7.0 Hz, 1H),1.63-1.56 (m, 2H), 1.45 (d, J=4.9 Hz, 3H), 1.26-1.16 (m, 3H), 0.83 (dt,J=10.2, 7.4 Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) 6-58.02; ESIMS m/z 596(M+H)⁺.

Example 25 Preparation of(Z)-3-(2-chloro-6-methylphenyl)-4-methyl-2-((E)-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)thiazolidin-4-ol(Compound 244C; Synthesis Method M)

Starting from(E)-N-(2-chloro-6-methylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide,and using conditions described in Example 23, the title compound wasisolated as a yellow solid (107 mg, 91%): mp 103° C. (dec); ¹H NMR (400MHz, CDCl₃) δ 8.57 (s, 1H), 8.22 (s, 1H), 8.18 (d, J=8.4 Hz, 2H),7.83-7.76 (m, 4H), 7.41-7.32 (m, 3H), 7.25-7.21 (m, 2H), 3.70-3.61 (m,1H), 3.53 (s, 1H), 3.30 (d, J=11.2 Hz, 1H), 2.49 (s, 3H), 1.51 (s, 3H);¹⁹F NMR (376 MHz, CDCl₃) δ −58.02; ESIMS m/z 588 (M+H)⁺.

Example 26 Preparation of(Z)-3-(4-methoxy-2-methylphenyl)-4-methyl-2-((E)-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)thiazolidin-4-ol(Compound 245C; Synthesis Method M)

Starting from(E)-N-(2-methyl-4-methoxyphenyl)-2-(4-(1-(4-(trifluoromethoxy)-phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide,and using conditions described in Example 23, the title compound wasisolated as a yellow solid (88 mg, 76%): mp 129° C. (dec); ¹H NMR (400MHz, CDCl₃) δ 8.57 (s, 1H), 8.25 (s, 1H), 8.18 (d, J=8.3 Hz, 2H),7.82-7.75 (m, 4H), 7.39 (t, J=8.8 Hz, 3H), 6.86-6.76 (m, 2H), 3.83 (s,3H), 3.52 (d, J=11.5 Hz, 1H), 3.43 (s, 1H), 3.31 (d, J=11.6 Hz, 1H),2.19 (s, 2H), 1.43 (s, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ −58.02; ESIMS m/z584 (M+H)⁺.

Example 27 Preparation of(Z)-3-(2-isopropylphenyl)-2-((E)-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)-4-(trifluoromethyl)thiazolidin-4-ol(Compound 246C; Synthesis Method M)

To a solution of(E)-N-(2-isopropylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide(351 mg, 0.67 mmol) in butanone (6.7 mL) was added3-bromo-1,1,1-trifluoroacetone (0.14 mL, 1.34 mmol) and triethylamine(0.19 mL, 1.34 mmol), and the reaction was stirred at 85° C. for 21hours. The mixture was allowed to cool to room temperature, transferredto a separatory funnel containing water (5 mL), and the aqueous mixtureextracted twice with dichloromethane. The organic extracts were filteredthrough a phase separator, adsorbed onto silica gel, and purified byflash chromatography (0-20% ethyl acetate/B, where B=1:1dichloromethane/hexanes) to provide a diastereomeric mixture (2:1) ofthe title compound as an orange solid (189 mg, 45%): mp 185-187° C.; ¹HNMR (400 MHz, CDCl₃, both diastereomers) δ 8.56 (m, 2H), 8.22-8.14 (m,6H), 7.83-7.75 (m, 8H), 7.49-7.34 (m, 10H), 7.32-7.23 (m, 2H), 4.22 (s,1H), 3.82 (dd, J=12.5, 4.8 Hz, 2H), 3.51 (d, J=13.2 Hz, 1H), 3.40 (d,J=12.3 Hz, 1H), 3.31 (s, 1H), 3.09 (tt, J=13.9, 7.0 Hz, 2H), 1.31-1.13(m, 12H); ¹⁹F NMR (376 MHz, CDCl₃) δ −58.02, −78.33, −78.77; ESIMS m/z636 (M+H)⁺.

Example 28 Preparation of(Z)-3-(2-(sec-butyl)phenyl)-2-((E)-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)-4-(trifluoromethyl)thiazolidin-4-ol(Compound 247C; Synthesis Method M)

To a solution of(E)-N-(2-(sec-butyl)phenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide(203 mg, 0.38 mmol) in butanone (3.8 mL) was added triethylamine (0.07mL, 0.49 mmol) and 3-bromo-1,1,1-trifluoroacetone (0.05 mL, 0.49 mmol),and the reaction was stirred at 85° C. for 20 hours, after which LC/MSanalysis showed minimal conversion. Additional triethylamine (0.03 mL,0.21 mmoL) and 3-bromo-1,1,1-trifluoroacetone (0.1 mL, 0.98 mmol) wereadded to the reaction mixture and the reaction was stirred at 90° C. foran additional 20 hours. The mixture was allowed to cool to roomtemperature, transferred to a separatory funnel containing water (5 mL),and extracted twice with dichloromethane. The organic extracts werefiltered through a phase separator, adsorbed onto silica gel, andpurified by flash chromatography (0-20% ethyl acetate/B, where B=1:1dichloromethane/hexanes). Further purification by reverse-phase flashchromatography (0-100% acetonitrile/water) provided the title compoundas an orange solid (16 mg, 7%): ¹H NMR (400 MHz, CDCl₃) δ 8.59-8.54 (m,1H), 8.30-8.13 (m, 3H), 7.79 (dd, J=8.6, 6.7 Hz, 4H), 7.45-7.34 (m, 5H),7.32-7.21 (m, 1H), 3.99 (s, 1H), 3.83 (d, J=12.2 Hz, 1H), 3.52-3.38 (m,1H), 2.82-2.75 (m, 1H), 1.27-1.26 (m, 1H), 1.21-1.12 (m, 3H), 0.97-0.75(m, 4H); ¹⁹F NMR (376 MHz, CDCl₃) δ −58.03, −78.23, −78.32, −78.76,−78.84; ESIMS m/z 650 (M+H)⁺.

Compounds 248-256, 258-262, and 264, shown in Table 3, were preparedaccording to the method described in Example 23 from the appropriatelysubstituted intermediates disclosed in Table 1. Characterization datafor these compounds is reported in Table 4.

Example 29 Preparation of(Z)-3-(2-isopropylphenyl)-4,5-dimethyl-2-((E)-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)thiazolidin-4-ol(Compound 257C)

To a solution of(E)-N-(2-isopropylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide(114 mg, 0.22 mmol) in butanone (2.2 mL) was added 3-bromo-2-butanone(0.03 mL, 0.28 mmol) and triethylamine (0.06 mL, 0.44 mmol), and thereaction was stirred at room temperature overnight. The reaction mixturewas directly applied to a silica gel cartridge and purified by flashchromatography (0-30% ethyl acetate/B, where B=1:1dichloromethane/hexanes) to provide the title compound as a yellow solid(108 mg, 84% yield): mp 140° C. (dec); ¹H NMR (400 MHz, CDCl₃) δ 8.57(s, 1H), 8.22-8.16 (m, 3H), 7.82-7.74 (m, 4H), 7.55-7.47 (m, 1H),7.42-7.35 (m, 4H), 7.29-7.24 (m, 1H), 3.92-2.96 (m, 3H), 1.57 (s, 1H),1.57-1.50 (m, 3H), 1.35-1.17 (m, 9H); ¹⁹F NMR (376 MHz, CDCl₃) δ −58.02;ESIMS m/z 595 ([M+H]⁺).

Example 30 Preparation of(Z)-3-(2-isopropylphenyl)-2-((E)-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)-4-(2-(trifluoromethyl)phenyl)thiazolidin-4-ol(Compound 263C)

A solution of(E)-N-(2-isopropylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide(0.30 g, 0.57 mmol) and 2-(trifluoromethyl)phenacyl bromide (0.22 g,0.85 mmol) in DCE (30 mL) was heated to reflux and stirred overnight.The reaction mixture was cooled to room temperature, diluted with ethylacetate (100 mL), washed with water (2×50 mL), washed with brinesolution (1×25 mL), and dried over anhydrous sodium sulfate. Thesolution was filtered, the filtrate concentrated, and the residuepurified by flash chromatography (0-100% ethyl acetate/hexanes) toprovide(Z)-3-(2-isopropylphenyl)-2-((E)-(4-(1-(4-(trifluoromethoxy)-phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)-4-(2-(trifluoromethyl)-phenyl)thiazolidin-4-olas a yellow solid (0.15 g, 38% yield): mp 115-117.5° C.; ¹H NMR (400MHz, CDCl₃) δ 8.59 (s, 1H), 8.33 (s, 1H), 8.24 (d, J=8.4 Hz, 2H), 8.13(s, 1H), 7.86-7.77 (m, 5H), 7.73 (d, J=7.2 Hz, 1H), 7.62 (dt, J=21.6,7.2 Hz, 2H), 7.40 (d, J=8.2 Hz, 2H), 7.37-7.28 (m, 3H), 7.24-7.17 (m,1H), 4.34 (s, 2H), 3.20 (dt, J=13.7, 6.8 Hz, 2H), 1.25 (d, J=6.9 Hz,6H); ¹⁹F NMR (376 MHz, CDCl₃) δ −57.99, −58.02; ESIMS m/z 711 ([M+H]⁺).

Example 31(E)-N-(2-cyclopentylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide(Compound I-35; Synthesis Methods N and C)

Step 1: Preparation of 1-(cyclopent-1-en-1-yl)-2-nitrobenzene (I-32,Method N)

To a mixture of 1-chloro-2-nitrobenzene (0.5 g, 3.2 mmol) and sodiumcarbonate (0.34 g, 3.2 mmol) in a 100 mL roundbottom flask equipped witha magnetic stir bar and nitrogen inlet were added water (3.2 mL),dioxane (13 mL) and2-(cyclopent-1-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.77mL, 3.8 mmol). The reaction flask was evacuated and purged with nitrogen(2×) prior to the addition of bis(triphenylphosphine)palladium(II)chloride (0.18 g, 0.25 mmol), and then evacuated and purged (3×)following the addition of the catalyst. The reaction was heated to 80°C. and stirred overnight. The reaction was cooled and filtered through apad of Celite® which was subsequently washed with water and ethylacetate. The phases were separated and the organic phase was dried bypassing it through a phase separator cartridge and concentrated. Theresidue was purified by flash column chromatography providing the titlecompound (0.56 g, 3.0 mmol, 93% yield) as a yellow oil: ¹H NMR (400 MHz,CDCl₃) δ 7.78-7.71 (m, 1H), 7.54-7.47 (m, 1H), 7.40-7.32 (m, 2H),5.86-5.82 (m, 1H), 2.63-2.55 (m, 2H), 2.55-2.47 (m, 2H), 2.09-1.98 (m,2H); ¹³C NMR (101 MHz, CDCl₃) δ 148.77, 139.96, 133.58, 132.08, 130.87,130.52, 127.55, 123.70, 35.31, 33.49, 24.05; ESIMS m/z 190 ([M+H]⁺).

Step 2: Preparation of 2-cyclopentylaniline (I-33, Method N)

To a solution of 1-(cyclopent-1-en-1-yl)-2-nitrobenzene (0.58 g, 3.0mmol) in ethyl acetate (30 mL) in a 200 mL roundbottom flask equippedwith a magnetic stir bar and nitrogen inlet was added palladium oncarbon (0.63 g, 0.30 mmol, 5%). The flask was evacuated and purged withnitrogen (3×), and then evacuated and placed under hydrogen (1atmosphere (atm)). The mixture was stirred at room temperatureovernight, filtered through a pad of Celite®, and the filter cake washedwith ethyl acetate. The filtrate was concentrated to provide the titlecompound (0.46 g, 2.9 mmol, 98% yield) as a clear and slightly red oil:¹H NMR (400 MHz, CDCl₃) δ 7.14 (dd, J=7.7, 1.3 Hz, 1H), 7.02 (td, J=7.6,1.5 Hz, 1H), 6.76 (td, J=7.4, 1.1 Hz, 1H), 6.68 (dd, J=7.8, 1.2 Hz, 1H),3.66 (bs, 2H), 3.04-2.92 (m, 1H), 2.13-1.98 (m, 2H), 1.88-1.58 (m, 6H);¹³C NMR (101 MHz, CDCl₃) δ 144.12, 130.34, 126.51, 125.95, 118.78,115.70, 39.89, 32.17, 25.21; ESIMS m/z 162 ([M+H]⁺).

Step 3: Preparation of N-(2-cyclopentylphenyl)hydrazinecarbothioamide(I-34, Method N)

To a biphasic solution of 2-cyclopentylaniline (0.46 g, 2.9 mmol) indichloromethane (10 mL) and water (4.8 mL) in a 100 mL roundbottom flaskequipped with a magnetic stir bar and nitrogen inlet was added sodiumhydrogencarbonate (0.73 g, 8.6 mmol) followed by thiophosgene (0.21 mL,2.8 mmol). The reaction was stirred at room temperature for 1 hour,filtered through a phase separator cartridge, and concentrated providingthe 1-cyclopentyl-2-isothiocyanatobenzene as a red oil which was usedwithout further purification. To a solution of the isothiocyanate inethanol (5.5 mL) in a 100 mL roundbottom flask was added hydrazinehydrate (0.15 mL, 3.1 mmol), and the reaction was stirred at roomtemperature overnight. The reaction mixture was diluted with hexanes andthe resulting solid was collected by filtration, washed with hexanes,and dried under house vacuum to provide the title compound (0.41 g, 1.7mmol, 63% yield) as a white solid: ¹H NMR (400 MHz, CDCl₃) δ 9.02 (bs,1H), 7.52 (bs, 1H), 7.41-7.18 (m, 4H), 4.06 (bs, 2H), 3.21-3.06 (m, 1H),2.04 (s, 2H), 1.90-1.74 (m, 2H), 1.74-1.58 (m, 4H); ESIMS m/z 236([M+H]⁺).

Step 4: Preparation of(E)-N-(2-cyclopentylphenyl)-2-(4-(1-(4-(trifluoro-methoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide(I-35, Method C)

To a mixture of4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzaldehyde(0.58 g, 1.7 mmol) and N-(2-cyclopentylphenyl)hydrazinecarbothioamide(0.41 g, 1.7 mmol) in a 100 mL roundbottom flask equipped with amagnetic stir bar and reflux condenser was added methanol (17 mL), andthe reaction was heated to 50° C. and stirred overnight. The reactionwas cooled to room temperature and the resulting solid was filtered,washed with methanol and dried under vacuum (25 in Hg) at 55° C. to givethe title compound (795 mg, 1.44 mmol, 83% yield) as a yellow solid: mp213-216° C.; ¹H NMR (400 MHz, CDCl₃) δ 9.45 (s, 1H), 9.11 (s, 1H), 8.60(s, 1H), 8.26 (d, J=8.4 Hz, 2H), 7.91 (s, 1H), 7.86-7.71 (m, 5H), 7.40(dd, J=8.8, 6.4 Hz, 3H), 7.35-7.27 (m, 2H), 3.22 (t, J=8.0 Hz, 1H), 2.13(d, J=2.5 Hz, 2H), 1.90-1.59 (m, 6H); ESIMS m/z 551 ([M+H]⁺).

Intermediate compounds I-36-I-55 and I-61-I-62, shown in Table 1, wereprepared according to the methods outlined in Example 29, Steps 1-4.Characterization data for these intermediates is shown in Table 2.

Example 32 Bioassays on Beet Armyworm (“BAW”) and Corn Earworm (“CEW”)

BAW has few effective parasites, diseases, or predators to lower itspopulation. BAW infests many weeds, trees, grasses, legumes, and fieldcrops. In various places, it is of economic concern upon asparagus,cotton, corn, soybeans, tobacco, alfalfa, sugar beets, peppers,tomatoes, potatoes, onions, peas, sunflowers, and citrus, among otherplants. CEW is known to attack corn and tomatoes, but it also attacksartichoke, asparagus, cabbage, cantaloupe, collards, cowpeas, cucumbers,eggplant, lettuce, lima beans, melon, okra, peas, peppers, potatoes,pumpkin, snap beans, spinach, squash, sweet potatoes, and watermelon,among other plants. CEW is also known to be resistant to certaininsecticides. Consequently, because of the above factors control ofthese pests is important. Furthermore, molecules that control thesepests are useful in controlling other pests.

Certain molecules disclosed in this document were tested against BAW andCEW using procedures described in the following examples. In thereporting of the results, the “BAW & CEW Rating Table” was used (SeeTable Section).

Bioassays on BAW (Spodoptera exigua)

Bioassays on BAW were conducted using a 128-well diet tray assay. One tofive second instar BAW larvae were placed in each well (3 mL) of thediet tray that had been previously filled with 1 mL of artificial dietto which 50 μg/cm² of the test compound (dissolved in 50 μL of 90:10acetone-water mixture) had been applied (to each of eight wells) andthen allowed to dry. Trays were covered with a clear self-adhesive coverand held at 25° C., 14:10 light-dark for five to seven days. Percentmortality was recorded for the larvae in each well; activity in theeight wells was then averaged. The results are indicated in the tableentitled “Table 5: Biological Results” (See Table Section).

Bioassays on CEW (Helicoverpa zea)

Bioassays on CEW were conducted using a 128-well diet tray assay. One tofive second instar CEW larvae were placed in each well (3 mL) of thediet tray that had been previously filled with 1 mL of artificial dietto which 50 μg/cm² of the test compound (dissolved in 50 μL of 90:10acetone-water mixture) had been applied (to each of eight wells) andthen allowed to dry. Trays were covered with a clear self-adhesive coverand held at 25° C., 14:10 light-dark for five to seven days. Percentmortality was recorded for the larvae in each well; activity in theeight wells was then averaged. The results are indicated in the tableentitled “Table 5: Biological Results” (See Table Section).

Example 33 Bioassays on Green Peach Aphid (“GPA”) (Myzus persicae)

GPA is the most significant aphid pest of peach trees, causing decreasedgrowth, shriveling of the leaves, and the death of various tissues. Itis also hazardous because it acts as a vector for the transport of plantviruses, such as potato virus Y and potato leafroll virus to members ofthe nightshade/potato family Solanaceae, and various mosaic viruses tomany other food crops. GPA attacks such plants as broccoli, burdock,cabbage, carrot, cauliflower, daikon, eggplant, green beans, lettuce,macadamia, papaya, peppers, sweet potatoes, tomatoes, watercress, andzucchini, among other plants. GPA also attacks many ornamental cropssuch as carnation, chrysanthemum, flowering white cabbage, poinsettia,and roses. GPA has developed resistance to many pesticides.

Certain molecules disclosed in this document were tested against GPAusing procedures described in the following example. In the reporting ofthe results, the “GPA Rating Table” was used (See Table Section).

Cabbage seedlings grown in 3-inch pots, with 2-3 small (3-5 cm) trueleaves, were used as test substrate. The seedlings were infested with20-50 GPA (wingless adult and nymph stages) one day prior to chemicalapplication. Four pots with individual seedlings were used for eachtreatment. Test compounds (2 mg) were dissolved in 2 mL ofacetone/methanol (1:1) solvent, forming stock solutions of 1000 ppm testcompound. The stock solutions were diluted 5× with 0.025% Tween 20 inH₂O to obtain the solution at 200 ppm test compound. A hand-heldaspirator-type sprayer was used for spraying a solution to both sides ofcabbage leaves until runoff. Reference plants (solvent check) weresprayed with the diluent only containing 20% by volume ofacetone/methanol (1:1) solvent. Treated plants were held in a holdingroom for three days at approximately 25° C. and ambient relativehumidity (RH) prior to grading. Evaluation was conducted by counting thenumber of live aphids per plant under a microscope. Percent Control wasmeasured by using Abbott's correction formula (W. S. Abbott, “A Methodof Computing the Effectiveness of an Insecticide” J. Econ. Entomol. 18(1925), pp. 265-267) as follows.Corrected % Control=100*(X−Y)/X

-   -   where    -   X=No. of live aphids on solvent check plants and    -   Y=No. of live aphids on treated plants

The results are indicated in the table entitled “Table 5: BiologicalResults” (See Table Section).

Pesticidally Acceptable Acid Addition Salts, Salt Derivatives, Solvates,Ester Derivatives, Polymorphs, Isotopes and Radionuclides

Molecules of Formulas One, Two and Three may be formulated intopesticidally acceptable acid addition salts. By way of a non-limitingexample, an amine function can form salts with hydrochloric,hydrobromic, sulfuric, phosphoric, acetic, benzoic, citric, malonic,salicylic, malic, fumaric, oxalic, succinic, tartaric, lactic, gluconic,ascorbic, maleic, aspartic, benzenesulfonic, methanesulfonic,ethanesulfonic, hydroxymethanesulfonic, and hydroxyethanesulfonic acids.Additionally, by way of a non-limiting example, an acid function canform salts including those derived from alkali or alkaline earth metalsand those derived from ammonia and amines. Examples of preferred cationsinclude sodium, potassium, and magnesium.

Molecules of Formulas One, Two and Three may be formulated into saltderivatives. By way of a non-limiting example, a salt derivative can beprepared by contacting a free base with a sufficient amount of thedesired acid to produce a salt. A free base may be regenerated bytreating the salt with a suitable dilute aqueous base solution such asdilute aqueous sodium hydroxide (NaOH), potassium carbonate, ammonia,and sodium bicarbonate. As an example, in many cases, a pesticide, suchas 2,4-D, is made more water-soluble by converting it to itsdimethylamine salt.

Molecules of Formulas One, Two and Three may be formulated into stablecomplexes with a solvent, such that the complex remains intact after thenon-complexed solvent is removed. These complexes are often referred toas “solvates.” However, it is particularly desirable to form stablehydrates with water as the solvent.

Molecules of Formulas One, Two and Three may be made into esterderivatives. These ester derivatives can then be applied in the samemanner as the invention disclosed in this document is applied.

Molecules of Formulas One, Two and Three may be made as various crystalpolymorphs. Polymorphism is important in the development ofagrochemicals since different crystal polymorphs or structures of thesame molecule can have vastly different physical properties andbiological performances.

Molecules of Formulas One, Two and Three may be made with differentisotopes. Of particular importance are molecules having ²H (also knownas deuterium) in place of ¹H.

Molecules of Formulas One, Two and Three may be made with differentradionuclides. Of particular importance are molecules having ¹⁴C.

Stereoisomers

Molecules of Formulas One, Two and Three may exist as one or morestereoisomers. Thus, certain molecules can be produced as racemicmixtures. It will be appreciated by those skilled in the art that onestereoisomer may be more active than the other stereoisomers. Individualstereoisomers may be obtained by known selective synthetic procedures,by conventional synthetic procedures using resolved starting materials,or by conventional resolution procedures.

Insecticides

Molecules of Formulas One, Two and Three may also be used in combination(such as, in a compositional mixture, or a simultaneous or sequentialapplication) with one or more of the followinginsecticides—1,2-dichloropropane, abamectin, acephate, acetamiprid,acethion, acetoprole, acrinathrin, acrylonitrile, alanycarb, aldicarb,aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb,alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan, amidithion,aminocarb, amiton, amiton oxalate, amitraz, anabasine, athidathion,azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate,barium hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensultap,beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin,bioethanomethrin, biopermethrin, bistrifluoron, borax, boric acid,bromfenvinfos, bromocyclen, bromo-DDT, bromophos, bromophos-ethyl,bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate,butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide,camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbontetrachloride, carbophenothion, carbosulfan, cartap, cartaphydrochloride, chlorantraniliprole, chlorbicyclen, chlordane,chlordecone, chlordimeform, chlordimeform hydrochloride, chlorethoxyfos,chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroform,chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos,chlorpyrifos-methyl, chlorthiophos, chromafenozide, cinerin I, cinerinII, cinerins, cismethrin, cloethocarb, closantel, clothianidin, copperacetoarsenite, copper arsenate, copper naphthenate, copper oleate,coumaphos, coumithoate, crotamiton, crotoxyphos, crufomate, cryolite,cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, cyclethrin,cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin,cyromazine, cythioate, DDT, decarbofuran, deltamethrin, demephion,demephion-O, demephion-S, demeton, demeton-methyl, demeton-O,demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulphon,diafenthiuron, dialifos, diatomaceous earth, diazinon, dicapthon,dichlofenthion, dichlorvos, dicresyl, dicrotophos, dicyclanil, dieldrin,diflubenzuron, dilor, dimefluthrin, dimefox, dimetan, dimethoate,dimethrin, dimethylvinphos, dimetilan, dinex, dinex-diclexine, dinoprop,dinosam, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion,disulfoton, dithicrofos, d-limonene, DNOC, DNOC-ammonium,DNOC-potassium, DNOC-sodium, doramectin, ecdysterone, emamectin,emamectin benzoate, EMPC, empenthrin, endosulfan, endothion, endrin,EPN, epofenonane, eprinomectin, esdepalléthrine, esfenvalerate, etaphos,ethiofencarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethylformate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethyleneoxide, etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor,fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb,fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion,fenthion, fenthion-ethyl, fenvalerate, fipronil, flometoquin,flonicamid, flubendiamide (additionally resolved isomers thereof),flucofuron, flucycloxuron, flucythrinate, flufenerim, flufenoxuron,flufenprox, flufiprole, flupyradifurone, fluvalinate, fonofos,formetanate, formetanate hydrochloride, formothion, formparanate,formparanate hydrochloride, fosmethilan, fospirate, fosthietan,fufenozide, furathiocarb, furethrin, gamma-cyhalothrin, gamma-HCH,halfenprox, halofenozide, HCH, HEOD, heptachlor, heptenophos,heterophos, hexaflumuron, HHDN, hydramethylnon, hydrogen cyanide,hydroprene, hyquincarb, imidacloprid, imiprothrin, indoxacarb,iodomethane, IPSP, isazofos, isobenzan, isocarbophos, isodrin,isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane, isothioate,isoxathion, ivermectin, jasmolin I, jasmolin II, jodfenphos, juvenilehormone I, juvenile hormone II, juvenile hormone III, kelevan,kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, leptophos,lindane, lirimfos, lufenuron, lythidathion, malathion, malonoben,mazidox, mecarbam, mecarphon, menazon, meperfluthrin, mephosfolan,mercurous chloride, mesulfenfos, metaflumizone, methacrifos,methamidophos, methidathion, methiocarb, methocrotophos, methomyl,methoprene, methothrin, methoxychlor, methoxyfenozide, methyl bromide,methyl isothiocyanate, methylchloroform, methylene chloride,metofluthrin, metolcarb, metoxadiazone, mevinphos, mexacarbate,milbemectin, milbemycin oxime, mipafox, mirex, molosultap,monocrotophos, monomehypo, monosultap, morphothion, moxidectin,naftalofos, naled, naphthalene, nicotine, nifluridide, nitenpyram,nithiazine, nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl,oxydemeton-methyl, oxydeprofos, oxydisulfoton, para-dichlorobenzene,parathion, parathion-methyl, penfluoron, pentachlorophenol, permethrin,phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan,phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phoxim-methyl,pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassiumarsenite, potassium thiocyanate, pp′-DDT, prallethrin, precocene I,precocene II, precocene III, primidophos, profenofos, profluralin,profluthrin, promacyl, promecarb, propaphos, propetamphos, propoxur,prothidathion, prothiofos, prothoate, protrifenbute, pymetrozine,pyraclofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I,pyrethrin II, pyrethrins, pyridaben, pyridalyl, pyridaphenthion,pyrifluquinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen,quassia, quinalphos, quinalphos-methyl, quinothion, rafoxanide,resmethrin, rotenone, ryania, sabadilla, schradan, selamectin,silafluofen, silica gel, sodium arsenite, sodium fluoride, sodiumhexafluorosilicate, sodium thiocyanate, sophamide, spinetoram, spinosad,spiromesifen, spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid,sulfotep, sulfoxaflor, sulfuryl fluoride, sulprofos, tau-fluvalinate,tazimcarb, TDE, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron,tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachloroethane,tetrachlorvinphos, tetramethrin, tetramethylfluthrin,theta-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocarboxime,thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon,thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin,tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarathene,triazamate, triazophos, trichlorfon, trichlormetaphos-3, trichloronat,trifenofos, triflumuron, trimethacarb, triprene, vamidothion,vaniliprole, XMC, xylylcarb, zeta-cypermethrin, and zolaprofos(collectively these commonly named insecticides are defined as the“Insecticide Group”).

Acaricides

Molecules of Formulas One, Two and Three may also be used in combination(such as, in a compositional mixture, or a simultaneous or sequentialapplication) with one or more of the following acaricides—acequinocyl,amidoflumet, arsenous oxide, azobenzene, azocyclotin, benomyl,benoxafos, benzoximate, benzyl benzoate, bifenazate, binapacryl,bromopropylate, chinomethionat, chlorbenside, chlorfenethol,chlorfenson, chlorfensulphide, chlorobenzilate, chloromebuform,chloromethiuron, chloropropylate, clofentezine, cyenopyrafen,cyflumetofen, cyhexatin, dichlofluanid, dicofol, dienochlor,diflovidazin, dinobuton, dinocap, dinocap-4, dinocap-6, dinocton,dinopenton, dinosulfon, dinoterbon, diphenyl sulfone, disulfuram,dofenapyn, etoxazole, fenazaquin, fenbutatin oxide, fenothiocarb,fenpyroximate, fenson, fentrifanil, fluacrypyrim, fluazuron,flubenzimine, fluenetil, flumethrin, fluorbenside, hexythiazox,mesulfen, MNAF, nikkomycins, proclonol, propargite, quintiofos,spirodiclofen, sulfuram, sulfur, tetradifon, tetranactin, tetrasul, andthioquinox (collectively these commonly named acaricides are defined asthe “Acaricide Group”).

Nematicides

Molecules of Formulas One, Two and Three may also be used in combination(such as, in a compositional mixture, or a simultaneous or sequentialapplication) with one or more of the followingnematicides—1,3-dichloropropene, benclothiaz, dazomet, dazomet-sodium,DBCP, DCIP, diamidafos, fluensulfone, fosthiazate, furfural, imicyafos,isamidofos, isazofos, metam, metam-ammonium, metam-potassium,metam-sodium, phosphocarb, and thionazin (collectively these commonlynamed nematicides are defined as the “Nematicide Group”)

Fungicides

Molecules of Formulas One, Two and Three may also be used in combination(such as, in a compositional mixture, or a simultaneous or sequentialapplication) with one or more of the followingfungicides—(3-ethoxypropyl)mercury bromide, 2-methoxyethylmercurychloride, 2-phenylphenol, 8-hydroxyquinoline sulfate,8-phenylmercurioxyquinoline, acibenzolar, acibenzolar-5-methyl,acypetacs, acypetacs-copper, acypetacs-zinc, aldimorph, allyl alcohol,ametoctradin, amisulbrom, ampropylfos, anilazine, aureofungin,azaconazole, azithiram, azoxystrobin, barium polysulfide, benalaxyl,benalaxyl-M, benodanil, benomyl, benquinox, bentaluron, benthiavalicarb,benthiavalicarb-isopropyl, benzalkonium chloride, benzamacril,benzamacril-isobutyl, benzamorf, benzohydroxamic acid, bethoxazin,binapacryl, biphenyl, bitertanol, bithionol, bixafen, blasticidin-S,Bordeaux mixture, boscalid, bromuconazole, bupirimate, Burgundy mixture,buthiobate, butylamine, calcium polysulfide, captafol, captan,carbamorph, carbendazim, carboxin, carpropamid, carvone, Cheshuntmixture, chinomethionat, chlobenthiazone, chloraniformethan, chloranil,chlorfenazole, chlorodinitronaphthalene, chloroneb, chloropicrin,chlorothalonil, chlorquinox, chlozolinate, climbazole, clotrimazole,copper acetate, copper carbonate, basic, copper hydroxide, coppernaphthenate, copper oleate, copper oxychloride, copper silicate, coppersulfate, copper zinc chromate, cresol, cufraneb, cuprobam, cuprousoxide, cyazofamid, cyclafuramid, cycloheximide, cyflufenamid, cymoxanil,cypendazole, cyproconazole, cyprodinil, dazomet, dazomet-sodium, DBCP,debacarb, decafentin, dehydroacetic acid, dichlofluanid, dichlone,dichlorophen, dichlozoline, diclobutrazol, diclocymet, diclomezine,diclomezine-sodium, dicloran, diethofencarb, diethyl pyrocarbonate,difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin,diniconazole, diniconazole-M, dinobuton, dinocap, dinocap-4, dinocap-6,dinocton, dinopenton, dinosulfon, dinoterbon, diphenylamine,dipyrithione, disulfuram, ditalimfos, dithianon, DNOC, DNOC-ammonium,DNOC-potassium, DNOC-sodium, dodemorph, dodemorph acetate, dodemorphbenzoate, dodicin, dodicin-sodium, dodine, drazoxolon, edifenphos,epoxiconazole, etaconazole, etem, ethaboxam, ethirimol, ethoxyquin,ethylmercury 2,3-dihydroxypropyl mercaptide, ethylmercury acetate,ethylmercury bromide, ethylmercury chloride, ethylmercury phosphate,etridiazole, famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol,fenbuconazole, fenfuram, fenhexamid, fenitropan, fenoxanil, fenpiclonil,fenpropidin, fenpropimorph, fentin, fentin chloride, fentin hydroxide,ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph,fluopicolide, fluopyram, fluoroimide, fluotrimazole, fluoxastrobin,fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil,flutriafol, fluxapyroxad, folpet, formaldehyde, fosetyl,fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, furcarbanil,furconazole, furconazole-cis, furfural, furmecyclox, furophanate,glyodin, griseofulvin, guazatine, halacrinate, hexachlorobenzene,hexachlorobutadiene, hexaconazole, hexylthiofos, hydrargaphen,hymexazol, imazalil, imazalil nitrate, imazalil sulfate, imibenconazole,iminoctadine, iminoctadine triacetate, iminoctadine trialbesilate,iodomethane, ipconazole, iprobenfos, iprodione, iprovalicarb,isoprothiolane, isopyrazam, isotianil, isovaledione, kasugamycin,kresoxim-methyl, mancopper, mancozeb, mandipropamid, maneb, mebenil,mecarbinzid, mepanipyrim, mepronil, meptyldinocap, mercuric chloride,mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam,metam-ammonium, metam-potassium, metam-sodium, metazoxolon, metconazole,methasulfocarb, methfuroxam, methyl bromide, methyl isothiocyanate,methylmercury benzoate, methylmercury dicyandiamide, methylmercurypentachlorophenoxide, metiram, metominostrobin, metrafenone,metsulfovax, milneb, myclobutanil, myclozolin,N-(ethylmercury)-p-toluenesulphonanilide, nabam, natamycin,nitrostyrene, nitrothal-isopropyl, nuarimol, OCH, octhilinone, ofurace,orysastrobin, oxadixyl, oxine-copper, oxpoconazole, oxpoconazolefumarate, oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen,pentachlorophenol, penthiopyrad, phenylmercuriurea, phenylmercuryacetate, phenylmercury chloride, phenylmercury derivative ofpyrocatechol, phenylmercury nitrate, phenylmercury salicylate,phosdiphen, phthalide, picoxystrobin, piperalin, polycarbamate,polyoxins, polyoxorim, polyoxorim-zinc, potassium azide, potassiumpolysulfide, potassium thiocyanate, probenazole, prochloraz,procymidone, propamocarb, propamocarb hydrochloride, propiconazole,propineb, proquinazid, prothiocarb, prothiocarb hydrochloride,prothioconazole, pyracarbolid, pyraclostrobin, pyraclostrobin,pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyridinitril,pyrifenox, pyrimethanil, pyriofenone, pyroquilon, pyroxychlor,pyroxyfur, quinacetol, quinacetol sulfate, quinazamid, quinconazole,quinoxyfen, quintozene, rabenzazole, salicylanilide, sedaxane,silthiofam, simeconazole, sodium azide, sodium orthophenylphenoxide,sodium pentachlorophenoxide, sodium polysulfide, spiroxamine,streptomycin, sulfur, sultropen, TCMTB, tebuconazole, tebufloquin,tecloftalam, tecnazene, tecoram, tetraconazole, thiabendazole,thiadifluor, thicyofen, thifluzamide, thiochlorfenphim, thiomersal,thiophanate, thiophanate-methyl, thioquinox, thiram, tiadinil, tioxymid,tolclofos-methyl, tolylfluanid, tolylmercury acetate, triadimefon,triadimenol, triamiphos, triarimol, triazbutil, triazoxide, tributyltinoxide, trichlamide, tricyclazole, tridemorph, trifloxystrobin,triflumizole, triforine, triticonazole, uniconazole, uniconazole-P,validamycin, valifenalate, vinclozolin, zarilamid, zinc naphthenate,zineb, ziram, zoxamide (collectively these commonly named fungicides aredefined as the “Fungicide Group”).

Herbicides

Molecules of Formulas One, Two and Three may also be used in combination(such as, in a compositional mixture, or a simultaneous or sequentialapplication) with one or more of the following herbicides—2,3,6-TBA,2,3,6-TBA-dimethylammonium, 2,3,6-TBA-sodium, 2,4,5-T,2,4,5-T-2-butoxypropyl, 2,4,5-T-2-ethylhexyl, 2,4,5-T-3-butoxypropyl,2,4,5-TB, 2,4,5-T-butomethyl, 2,4,5-T-butotyl, 2,4,5-T-butyl,2,4,5-T-isobutyl, 2,4,5-T-isoctyl, 2,4,5-T-isopropyl, 2,4,5-T-methyl,2,4,5-T-pentyl, 2,4,5-T-sodium, 2,4,5-T-triethylammonium,2,4,5-T-trolamine, 2,4-D, 2,4-D-2-butoxypropyl, 2,4-D-2-ethylhexyl,2,4-D-3-butoxypropyl, 2,4-D-ammonium, 2,4-DB, 2,4-DB-butyl,2,4-DB-dimethylammonium, 2,4-DB-isoctyl, 2,4-DB-potassium,2,4-DB-sodium, 2,4-D-butotyl, 2,4-D-butyl, 2,4-D-diethylammonium,2,4-D-dimethylammonium, 2,4-D-diolamine, 2,4-D-dodecylammonium, 2,4-DEB,2,4-DEP, 2,4-D-ethyl, 2,4-D-heptylammonium, 2,4-D-isobutyl,2,4-D-isoctyl, 2,4-D-isopropyl, 2,4-D-isopropylammonium, 2,4-D-lithium,2,4-D-meptyl, 2,4-D-methyl, 2,4-D-octyl, 2,4-D-pentyl, 2,4-D-potassium,2,4-D-propyl, 2,4-D-sodium, 2,4-D-tefuryl, 2,4-D-tetradecylammonium,2,4-D-triethylammonium, 2,4-D-tris(2-hydroxypropyl)ammonium,2,4-D-trolamine, 3,4-DA, 3,4-DB, 3,4-DP, 4-CPA, 4-CPB, 4-CPP,acetochlor, acifluorfen, acifluorfen-methyl, acifluorfen-sodium,aclonifen, acrolein, alachlor, allidochlor, alloxydim, alloxydim-sodium,allyl alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone,amidosulfuron, aminocyclopyrachlor, aminocyclopyrachlor-methyl,aminocyclopyrachlor-potassium, aminopyralid, aminopyralid-potassium,aminopyralid-tris(2-hydroxypropyl)ammonium, amiprofos-methyl, amitrole,ammonium sulfamate, anilofos, anisuron, asulam, asulam-potassium,asulam-sodium, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne,barban, BCPC, beflubutamid, benazolin, benazolin-dimethylammonium,benazolin-ethyl, benazolin-potassium, bencarbazone, benfluralin,benfuresate, bensulfuron, bensulfuron-methyl, bensulide, bentazone,bentazone-sodium, benzadox, benzadox-ammonium, benzfendizone, benzipram,benzobicyclon, benzofenap, benzofluor, benzoylprop, benzoylprop-ethyl,benzthiazuron, bicyclopyrone, bifenox, bilanafos, bilanafos-sodium,bispyribac, bispyribac-sodium, borax, bromacil, bromacil-lithium,bromacil-sodium, bromobonil, bromobutide, bromofenoxim, bromoxynil,bromoxynil butyrate, bromoxynil heptanoate, bromoxynil octanoate,bromoxynil-potassium, brompyrazon, butachlor, butafenacil, butamifos,butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon,butylate, cacodylic acid, cafenstrole, calcium chlorate, calciumcyanamide, cambendichlor, carbasulam, carbetamide, carboxazole,carfentrazone, carfentrazone-ethyl, CDEA, CEPC, chlomethoxyfen,chloramben, chloramben-ammonium, chloramben-diolamine,chloramben-methyl, chloramben-methylammonium, chloramben-sodium,chloranocryl, chlorazifop, chlorazifop-propargyl, chlorazine,chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenac-sodium,chlorfenprop, chlorfenprop-methyl, chlorflurazole, chlorflurenol,chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl,chlomitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil,chlorprocarb, chlorpropham, chlorsulfuron, chlorthal,chlorthal-dimethyl, chlorthal-monomethyl, chlorthiamid, cinidon-ethyl,cinmethylin, cinosulfuron, cisanilide, clethodim, cliodinate,clodinafop, clodinafop-propargyl, clofop, clofop-isobutyl, clomazone,clomeprop, cloprop, cloproxydim, clopyralid, clopyralid-methyl,clopyralid-olamine, clopyralid-potassium,clopyralid-tris(2-hydroxypropyl)ammonium, cloransulam,cloransulam-methyl, CMA, copper sulfate, CPMF, CPPC, credazine, cresol,cumyluron, cyanamide, cyanatryn, cyanazine, cycloate, cyclosulfamuron,cycloxydim, cycluron, cyhalofop, cyhalofop-butyl, cyperquat, cyperquatchloride, cyprazine, cyprazole, cypromid, daimuron, dalapon,dalapon-calcium, dalapon-magnesium, dalapon-sodium, dazomet,dazomet-sodium, delachlor, desmedipham, desmetryn, di-allate, dicamba,dicamba-dimethylammonium, dicamba-diolamine, dicamba-isopropylammonium,dicamba-methyl, dicamba-olamine, dicamba-potassium, dicamba-sodium,dicamba-trolamine, dichlobenil, dichloralurea, dichlormate, dichlorprop,dichlorprop-2-ethylhexyl, dichlorprop-butotyl,dichlorprop-dimethylammonium, dichlorprop-ethylammonium,dichlorprop-isoctyl, dichlorprop-methyl, dichlorprop-P,dichlorprop-P-dimethylammonium, dichlorprop-potassium,dichlorprop-sodium, diclofop, diclofop-methyl, diclosulam, diethamquat,diethamquat dichloride, diethatyl, diethatyl-ethyl, difenopenten,difenopenten-ethyl, difenoxuron, difenzoquat, difenzoquat metilsulfate,diflufenican, diflufenzopyr, diflufenzopyr-sodium, dimefuron,dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P,dimexano, dimidazon, dinitramine, dinofenate, dinoprop, dinosam,dinoseb, dinoseb acetate, dinoseb-ammonium, dinoseb-diolamine,dinoseb-sodium, dinoseb-trolamine, dinoterb, dinoterb acetate,diphacinone-sodium, diphenamid, dipropetryn, diquat, diquat dibromide,disul, disul-sodium, dithiopyr, diuron, DMPA, DNOC, DNOC-ammonium,DNOC-potassium, DNOC-sodium, DSMA, EBEP, eglinazine, eglinazine-ethyl,endothal, endothal-diammonium, endothal-dipotassium, endothal-disodium,epronaz, EPTC, erbon, esprocarb, ethalfluralin, ethametsulfuron,ethametsulfuron-methyl, ethidimuron, ethiolate, ethofumesate, ethoxyfen,ethoxyfen-ethyl, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD,fenasulam, fenoprop, fenoprop-3-butoxypropyl, fenoprop-butomethyl,fenoprop-butotyl, fenoprop-butyl, fenoprop-isoctyl, fenoprop-methyl,fenoprop-potassium, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P,fenoxaprop-P-ethyl, fenoxasulfone, fenteracol, fenthiaprop,fenthiaprop-ethyl, fentrazamide, fenuron, fenuron TCA, ferrous sulfate,flamprop, flamprop-isopropyl, flamprop-M, flamprop-methyl,flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam,fluazifop, fluazifop-butyl, fluazifop-methyl, fluazifop-P,fluazifop-P-butyl, fluazolate, flucarbazone, flucarbazone-sodium,flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr,flufenpyr-ethyl, flumetsulam, flumezin, flumiclorac, flumiclorac-pentyl,flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen,fluoroglycofen-ethyl, fluoromidine, fluoronitrofen, fluothiuron,flupoxam, flupropacil, flupropanate, flupropanate-sodium,flupyrsulfuron, flupyrsulfuron-methyl-sodium, fluridone,fluorochloridone, fluoroxypyr, fluoroxypyr-butomethyl,fluoroxypyr-meptyl, flurtamone, fluthiacet, fluthiacet-methyl,fomesafen, fomesafen-sodium, foramsulfuron, fosamine, fosamine-ammonium,furyloxyfen, glufosinate, glufosinate-ammonium, glufosinate-P,glufosinate-P-ammonium, glufosinate-P-sodium, glyphosate,glyphosate-diammonium, glyphosate-dimethylammonium,glyphosate-isopropylammonium, glyphosate-monoammonium,glyphosate-potassium, glyphosate-sesquisodium, glyphosate-trimesium,halosafen, halosulfuron, halosulfuron-methyl, haloxydine, haloxyfop,haloxyfop-etotyl, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-etotyl,haloxyfop-P-methyl, haloxyfop-sodium, hexachloroacetone, hexaflurate,hexazinone, imazamethabenz, imazamethabenz-methyl, imazamox,imazamox-ammonium, imazapic, imazapic-ammonium, imazapyr,imazapyr-isopropylammonium, imazaquin, imazaquin-ammonium,imazaquin-methyl, imazaquin-sodium, imazethapyr, imazethapyr-ammonium,imazosulfuron, indanofan, indaziflam, iodobonil, iodomethane,iodosulfuron, iodosulfuron-methyl-sodium, ioxynil, ioxynil octanoate,ioxynil-lithium, ioxynil-sodium, ipazine, ipfencarbazone, iprymidam,isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin,isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole,isoxapyrifop, karbutilate, ketospiradox, lactofen, lenacil, linuron,MAA, MAMA, MCPA, MCPA-2-ethylhexyl, MCPA-butotyl, MCPA-butyl,MCPA-dimethylammonium, MCPA-diolamine, MCPA-ethyl, MCPA-isobutyl,MCPA-isoctyl, MCPA-isopropyl, MCPA-methyl, MCPA-olamine, MCPA-potassium,MCPA-sodium, MCPA-thioethyl, MCPA-trolamine, MCPB, MCPB-ethyl,MCPB-methyl, MCPB-sodium, mecoprop, mecoprop-2-ethylhexyl,mecoprop-dimethylammonium, mecoprop-diolamine, mecoprop-ethadyl,mecoprop-isoctyl, mecoprop-methyl, mecoprop-P,mecoprop-P-dimethylammonium, mecoprop-P-isobutyl, mecoprop-potassium,mecoprop-P-potassium, mecoprop-sodium, mecoprop-trolamine, medinoterb,medinoterb acetate, mefenacet, mefluidide, mefluidide-diolamine,mefluidide-potassium, mesoprazine, mesosulfuron, mesosulfuron-methyl,mesotrione, metam, metam-ammonium, metamifop, metamitron,metam-potassium, metam-sodium, metazachlor, metazosulfuron, metflurazon,methabenzthiazuron, methalpropalin, methazole, methiobencarb,methiozolin, methiuron, methometon, methoprotryne, methyl bromide,methyl isothiocyanate, methyldymron, metobenzuron, metolachlor,metosulam, metoxuron, metribuzin, metsulfuron, metsulfuron-methyl,molinate, monalide, monisouron, monochloroacetic acid, monolinuron,monuron, monuron TCA, morfamquat, morfamquat dichloride, MSMA,naproanilide, napropamide, naptalam, naptalam-sodium, neburon,nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen,norflurazon, noruron, OCH, orbencarb, ortho-dichlorobenzene,orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon,oxapyrazon-dimolamine, oxapyrazon-sodium, oxasulfuron, oxaziclomefone,oxyfluorfen, parafluoron, paraquat, paraquat dichloride, paraquatdimetilsulfate, pebulate, pelargonic acid, pendimethalin, penoxsulam,pentachlorophenol, pentanochlor, pentoxazone, perfluidone, pethoxamid,phenisopham, phenmedipham, phenmedipham-ethyl, phenobenzuron,phenylmercury acetate, picloram, picloram-2-ethylhexyl,picloram-isoctyl, picloram-methyl, picloram-olamine, picloram-potassium,picloram-triethylammonium, picloram-tris(2-hydroxypropyl)ammonium,picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide,potassium cyanate, pretilachlor, primisulfuron, primisulfuron-methyl,procyazine, prodiamine, profluazol, profluralin, profoxydim,proglinazine, proglinazine-ethyl, prometon, prometryn, propachlor,propanil, propaquizafop, propazine, propham, propisochlor,propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron, propyzamide,prosulfalin, prosulfocarb, prosulfuron, proxan, proxan-sodium,prynachlor, pydanon, pyraclonil, pyraflufen, pyraflufen-ethyl,pyrasulfotole, pyrazolynate, pyrazosulfuron, pyrazosulfuron-ethyl,pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate,pyriftalid, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac,pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac,quinoclamine, quinonamid, quizalofop, quizalofop-ethyl, quizalofop-P,quizalofop-P-ethyl, quizalofop-P-tefuryl, rhodethanil, rimsulfuron,saflufenacil, sebuthylazine, secbumeton, sethoxydim, siduron, simazine,simeton, simetryn, SMA, S-metolachlor, sodium arsenite, sodium azide,sodium chlorate, sulcotrione, sulfallate, sulfentrazone, sulfometuron,sulfometuron-methyl, sulfosulfuron, sulfuric acid, sulglycapin, swep,TCA, TCA-ammonium, TCA-calcium, TCA-ethadyl, TCA-magnesium, TCA-sodium,tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim,terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn,tetrafluoron, thenylchlor, thiazafluoron, thiazopyr, thidiazimin,thidiazuron, thiencarbazone, thiencarbazone-methyl, thifensulfuron,thifensulfuron-methyl, thiobencarb, tiocarbazil, tioclorim, topramezone,tralkoxydim, tri-allate, triasulfuron, triaziflam, tribenuron,tribenuron-methyl, tricamba, triclopyr, triclopyr-butotyl,triclopyr-ethyl, triclopyr-triethylammonium, tridiphane, trietazine,trifloxysulfuron, trifloxysulfuron-sodium, trifluralin, triflusulfuron,triflusulfuron-methyl, trifop, trifop-methyl, trifopsime,trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron,vernolate, xylachlor, (collectively these commonly named herbicides aredefined as the “Herbicide Group”).

Biopesticides

Molecules of Formulas One, Two and Three may also be used in combination(such as in a compositional mixture, or a simultaneous or sequentialapplication) with one or more biopesticides. The term “biopesticide” isused for microbial biological pest control agents that are applied in asimilar manner to chemical pesticides. Commonly these are bacterial, butthere are also examples of fungal control agents, including Trichodermaspp. and Ampelomyces quisqualis (a control agent for grape powderymildew). Bacillus subtilis are used to control plant pathogens. Weedsand rodents have also been controlled with microbial agents. Onewell-known insecticide example is Bacillus thuringiensis, a bacterialdisease of Lepidoptera, Coleoptera, and Diptera. Because it has littleeffect on other organisms, it is considered more environmentallyfriendly than synthetic pesticides. Biological insecticides includeproducts based on:

1. entomopathogenic fungi (e.g. Metarhizium anisopliae);

2. entomopathogenic nematodes (e.g. Steinemema feltiae); and

3. entomopathogenic viruses (e.g. Cydia pomonella granulovirus).

Other examples of entomopathogenic organisms include, but are notlimited to, baculoviruses, bacteria and other prokaryotic organisms,fungi, protozoa and Microsproridia. Biologically derived insecticidesinclude, but not limited to, rotenone, veratridine, as well as microbialtoxins; insect tolerant or resistant plant varieties; and organismsmodified by recombinant DNA technology to either produce insecticides orto convey an insect resistant property to the genetically modifiedorganism. In one embodiment, the Molecules of Formula One, Two or Threemay be used with one or more biopesticides in the area of seedtreatments and soil amendments. The Manual of Biocontrol Agents gives areview of the available biological insecticide (and other biology-basedcontrol) products. Copping L. G. (ed.) (2004). The Manual of BiocontrolAgents (formerly the Biopesticide Manual) 3rd Edition. British CropProduction Council (BCPC), Farnham, Surrey UK.

Other Active Compounds

Molecules of Formulas One, Two and Three may also be used in combination(such as in a compositional mixture, or a simultaneous or sequentialapplication) with one or more of the following:

-   1.    3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-oxa-1-azaspiro[4,5]dec-3-en-2-one;-   2.    3-(4′-chloro-2,4-dimethyl[1,1′-biphenyl]-3-yl)-4-hydroxy-8-oxa-1-azaspiro[4,5]dec-3-en-2-one;-   3. 4-[[(6-chloro-3-pyridinyl)methyl]methylamino]-2(5H)-furanone;-   4.    4-[[(6-chloro-3-pyridinyl)methyl]cyclopropylamino]-2(5H)-furanone;-   5.    3-chloro-N-2-[(1S)-1-methyl-2-(methylsulfonyl)ethyl]-N1-[2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-1,2-benzenedicarboxamide;-   6. 2-cyano-N-ethyl-4-fluoro-3-methoxy-benenesulfonamide;-   7. 2-cyano-N-ethyl-3-methoxy-benzenesulfonamide;-   8. 2-cyano-3-difluoromethoxy-N-ethyl-4-fluoro-benzenesulfonamide;-   9. 2-cyano-3-fluoromethoxy-N-ethyl-benzenesulfonamide;-   10. 2-cyano-6-fluoro-3-methoxy-N,N-dimethyl-benzenesulfonamide;-   11. 2-cyano-N-ethyl-6-fluoro-3-methoxy-N-methyl-benzenesulfonamide;-   12. 2-cyano-3-difluoromethoxy-N,N-dimethylbenzenesulfon-amide;-   13.    3-(difluoromethyl)-N-[2-(3,3-dimethylbutyl)phenyl]-1-methyl-1H-pyrazole-4-carboxamide;-   14.    N-ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)    hydrazone;-   15.    N-ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)    hydrazone nicotine;-   16.    O-{(E-)-[2-(4-chloro-phenyl)-2-cyano-1-(2-trifluoromethylphenyl)-vinyl]}    S-methyl thiocarbonate;-   17.    (E)-N-1-[(2-chloro-1,3-thiazol-5-ylmethyl)]-N2-cyano-N-1-methylacetamidine;-   18.    1-(6-chloropyridin-3-ylmethyl)-7-methyl-8-nitro-1,2,3,5,6,7-hexahydro-imidazo[1,2-a]pyridin-5-ol;-   19. 4-[4-chlorophenyl-(2-butylidine-hydrazono)methyl)]phenyl    mesylate; and-   20.    N-Ethyl-2,2-dichloro-1-methylcyclopropanecarboxamide-2-(2,6-dichloro-alpha,alpha,alpha-trifluoro-p-tolyl)hydrazone.

Molecules of Formulas One, Two and Three may also be used in combination(such as in a compositional mixture, or a simultaneous or sequentialapplication) with one or more compounds in the following groups:algicides, antifeedants, avicides, bactericides, bird repellents,chemosterilants, herbicide safeners, insect attractants, insectrepellents, mammal repellents, mating disrupters, molluscicides, plantactivators, plant growth regulators, rodenticides, and/or virucides(collectively these commonly named groups are defined as the “AIGroup”). It should be noted that compounds falling within the AI Group,Insecticide Group, Fungicide Group, Herbicide Group, Acaricide Group, orNematicide Group might be in more than one group, because of multipleactivities the compound has. For more information consult the“COMPENDIUM OF PESTICIDE COMMON NAMES” located athttp://www.alanwood.net/pesticides/index.html. Also consult “THEPESTICIDE MANUAL” 14th Edition, edited by C D S Tomlin, copyright 2006by British Crop Production Council, or its prior or more recenteditions.

Synergistic Mixtures and Synergists

Molecules of Formulas One, Two and Three may be used with the compoundsin the Insecticide Group to form synergistic mixtures where the mode ofaction of such compounds compared to the mode of action of the Moleculesof Formula One and Two are the same, similar, or different. Examples ofmodes of action include, but are not limited to: acetylcholinesteraseinhibitor; sodium channel modulator; chitin biosynthesis inhibitor;GABA-gated chloride channel antagonist; GABA and glutamate-gatedchloride channel agonist; acetylcholine receptor agonist; MET Iinhibitor; Mg-stimulated ATPase inhibitor; nicotinic acetylcholinereceptor; Midgut membrane disrupter; oxidative phosphorylationdisrupter, and ryanodine receptor (RyRs). Additionally, Molecules ofFormula One and Two may be used with compounds in the Fungicide Group,Acaricide Group, Herbicide Group, or Nematicide Group to formsynergistic mixtures. Furthermore, Molecules of Formulas One, Two andThree may be used with other active compounds, such as the compoundsunder the heading “OTHER ACTIVE COMPOUNDS”, algicides, avicides,bactericides, molluscicides, rodenticides, virucides, herbicidesafeners, adjuvants, and/or surfactants to form synergistic mixtures.Generally, weight ratios of the Molecules of Formulas One, Two and Threein a synergistic mixture with another compound are from about 10:1 toabout 1:10, preferably from about 5:1 to about 1:5, and more preferablyfrom about 3:1, and even more preferably about 1:1. Additionally, thefollowing compounds are known as synergists and may be used with themolecules disclosed in Formula One: piperonyl butoxide, piprotal, propylisome, sesamex, sesamolin, sulfoxide, and tribufos (collectively thesesynergists are defined as the “Synergists Group”).

Formulations

A pesticide is rarely suitable for application in its pure form. It isusually necessary to add other substances so that the pesticide can beused at the required concentration and in an appropriate form,permitting ease of application, handling, transportation, storage, andmaximum pesticide activity. Thus, pesticides are formulated into, forexample, baits, concentrated emulsions, dusts, emulsifiableconcentrates, fumigants, gels, granules, microencapsulations, seedtreatments, suspension concentrates, suspoemulsions, tablets, watersoluble liquids, water dispersible granules or dry flowables, wettablepowders, and ultra low volume solutions. For further information onformulation types see “Catalogue of Pesticide Formulation Types andInternational Coding System” Technical Monograph n° 2, 5th Edition byCropLife International (2002).

Pesticides are applied most often as aqueous suspensions or emulsionsprepared from concentrated formulations of such pesticides. Suchwater-soluble, water-suspendable, or emulsifiable formulations areeither solids, usually known as wettable powders, or water dispersiblegranules, or liquids usually known as emulsifiable concentrates, oraqueous suspensions. Wettable powders, which may be compacted to formwater dispersible granules, comprise an intimate mixture of thepesticide, a carrier, and surfactants. The concentration of thepesticide is usually from about 10% to about 90% by weight. The carrieris usually chosen from among the attapulgite clays, the montmorilloniteclays, the diatomaceous earths, or the purified silicates. Effectivesurfactants, comprising from about 0.5% to about 10% of the wettablepowder, are found among sulfonated lignins, condensednaphthalenesulfonates, naphthalenesulfonates, alkylbenzenesulfonates,alkyl sulfates, and non-ionic surfactants such as ethylene oxide adductsof alkyl phenols.

Emulsifiable concentrates of pesticides comprise a convenientconcentration of a pesticide, such as from about 50 to about 500 gramsper liter of liquid dissolved in a carrier that is either a watermiscible solvent or a mixture of water-immiscible organic solvent andemulsifiers. Useful organic solvents include aromatics, especiallyxylenes and petroleum fractions, especially the high-boilingnaphthalenic and olefinic portions of petroleum such as heavy aromaticnaphtha. Other organic solvents may also be used, such as the terpenicsolvents including rosin derivatives, aliphatic ketones such ascyclohexanone, and complex alcohols such as 2-ethoxyethanol. Suitableemulsifiers for emulsifiable concentrates are chosen from conventionalanionic and non-ionic surfactants.

Aqueous suspensions comprise suspensions of water-insoluble pesticidesdispersed in an aqueous carrier at a concentration in the range fromabout 5% to about 50% by weight. Suspensions are prepared by finelygrinding the pesticide and vigorously mixing it into a carrier comprisedof water and surfactants. Ingredients, such as inorganic salts andsynthetic or natural gums may also be added, to increase the density andviscosity of the aqueous carrier. It is often most effective to grindand mix the pesticide at the same time by preparing the aqueous mixtureand homogenizing it in an implement such as a sand mill, ball mill, orpiston-type homogenizer.

Pesticides may also be applied as granular compositions that areparticularly useful for applications to the soil. Granular compositionsusually contain from about 0.5% to about 10% by weight of the pesticide,dispersed in a carrier that comprises clay or a similar substance. Suchcompositions are usually prepared by dissolving the pesticide in asuitable solvent and applying it to a granular carrier which has beenpre-formed to the appropriate particle size, in the range of from about0.5 to about 3 mm. Such compositions may also be formulated by making adough or paste of the carrier and compound and crushing and drying toobtain the desired granular particle size.

Dusts containing a pesticide are prepared by intimately mixing thepesticide in powdered form with a suitable dusty agricultural carrier,such as kaolin clay, ground volcanic rock, and the like. Dusts cansuitably contain from about 1% to about 10% of the pesticide. They canbe applied as a seed dressing or as a foliage application with a dustblower machine.

It is equally practical to apply a pesticide in the form of a solutionin an appropriate organic solvent, usually petroleum oil, such as thespray oils, which are widely used in agricultural chemistry.

Pesticides can also be applied in the form of an aerosol composition. Insuch compositions the pesticide is dissolved or dispersed in a carrier,which is a pressure-generating propellant mixture. The aerosolcomposition is packaged in a container from which the mixture isdispensed through an atomizing valve.

Pesticide baits are formed when the pesticide is mixed with food or anattractant or both. When the pests eat the bait they also consume thepesticide. Baits may take the form of granules, gels, flowable powders,liquids, or solids. They can be used in pest harborages.

Fumigants are pesticides that have a relatively high vapor pressure andhence can exist as a gas in sufficient concentrations to kill pests insoil or enclosed spaces. The toxicity of the fumigant is proportional toits concentration and the exposure time. They are characterized by agood capacity for diffusion and act by penetrating the pest'srespiratory system or being absorbed through the pest's cuticle.Fumigants are applied to control stored product pests under gas proofsheets, in gas sealed rooms or buildings or in special chambers.

Pesticides can be microencapsulated by suspending the pesticideparticles or droplets in plastic polymers of various types. By alteringthe chemistry of the polymer or by changing factors in the processing,microcapsules can be formed of various sizes, solubility, wallthicknesses, and degrees of penetrability. These factors govern thespeed with which the active ingredient within is released, which inturn, affects the residual performance, speed of action, and odor of theproduct.

Oil solution concentrates are made by dissolving pesticide in a solventthat will hold the pesticide in solution. Oil solutions of a pesticideusually provide faster knockdown and kill of pests than otherformulations due to the solvents themselves having pesticidal action andthe dissolution of the waxy covering of the integument increasing thespeed of uptake of the pesticide. Other advantages of oil solutionsinclude better storage stability, better penetration of crevices, andbetter adhesion to greasy surfaces.

Another embodiment is an oil-in-water emulsion, wherein the emulsioncomprises oily globules which are each provided with a lamellar liquidcrystal coating and are dispersed in an aqueous phase, wherein each oilyglobule comprises at least one compound which is agriculturally active,and is individually coated with a monolamellar or oligolamellar layercomprising: (1) at least one non-ionic lipophilic surface-active agent,(2) at least one non-ionic hydrophilic surface-active agent and (3) atleast one ionic surface-active agent, wherein the globules having a meanparticle diameter of less than 800 nanometers. Further information onthe embodiment is disclosed in U.S. patent publication 20070027034published Feb. 1, 2007, having patent application Ser. No. 11/495,228.For ease of use, this embodiment will be referred to as “OIWE”.

For further information consult “Insect Pest Management” 2nd Edition byD. Dent, copyright CAB International (2000). Additionally, for moredetailed information consult “Handbook of Pest Control—The Behavior,Life History, and Control of Household Pests” by Arnold Mallis, 9thEdition, copyright 2004 by GIE Media Inc.

Other Formulation Components

Generally, when the molecules disclosed in Formulas One, Two and Threeare used in a formulation, such formulation can also contain othercomponents. These components include, but are not limited to, (this is anon-exhaustive and non-mutually exclusive list) wetters, spreaders,stickers, penetrants, buffers, sequestering agents, drift reductionagents, compatibility agents, anti-foam agents, cleaning agents, andemulsifiers. A few components are described forthwith.

A wetting agent is a substance that when added to a liquid increases thespreading or penetration power of the liquid by reducing the interfacialtension between the liquid and the surface on which it is spreading.Wetting agents are used for two main functions in agrochemicalformulations: during processing and manufacture to increase the rate ofwetting of powders in water to make concentrates for soluble liquids orsuspension concentrates; and during mixing of a product with water in aspray tank to reduce the wetting time of wettable powders and to improvethe penetration of water into water-dispersible granules. Examples ofwetting agents used in wettable powder, suspension concentrate, andwater-dispersible granule formulations are: sodium lauryl sulfate;sodium dioctyl sulfosuccinate; alkyl phenol ethoxylates; and aliphaticalcohol ethoxylates.

A dispersing agent is a substance which adsorbs onto the surface ofparticles and helps to preserve the state of dispersion of the particlesand prevents them from reaggregating. Dispersing agents are added toagrochemical formulations to facilitate dispersion and suspension duringmanufacture, and to ensure the particles redisperse into water in aspray tank. They are widely used in wettable powders, suspensionconcentrates and water-dispersible granules. Surfactants that are usedas dispersing agents have the ability to adsorb strongly onto a particlesurface and provide a charged or steric barrier to reaggregation ofparticles. The most commonly used surfactants are anionic, non-ionic, ormixtures of the two types. For wettable powder formulations, the mostcommon dispersing agents are sodium lignosulfonates. For suspensionconcentrates, very good adsorption and stabilization are obtained usingpolyelectrolytes, such as sodium naphthalene sulfonate formaldehydecondensates. Tristyrylphenol ethoxylate phosphate esters are also used.Non-ionics such as alkylarylethylene oxide condensates and EO-PO blockcopolymers are sometimes combined with anionics as dispersing agents forsuspension concentrates. In recent years, new types of very highmolecular weight polymeric surfactants have been developed as dispersingagents. These have very long hydrophobic ‘backbones’ and a large numberof ethylene oxide chains forming the ‘teeth’ of a ‘comb’ surfactant.These high molecular weight polymers can give very good long-termstability to suspension concentrates because the hydrophobic backboneshave many anchoring points onto the particle surfaces. Examples ofdispersing agents used in agrochemical formulations are: sodiumlignosulfonates; sodium naphthalene sulfonate formaldehyde condensates;tristyrylphenol ethoxylate phosphate esters; aliphatic alcoholethoxylates; alkyl ethoxylates; EO-PO block copolymers; and graftcopolymers.

An emulsifying agent is a substance which stabilizes a suspension ofdroplets of one liquid phase in another liquid phase. Without theemulsifying agent the two liquids would separate into two immiscibleliquid phases. The most commonly used emulsifier blends containalkylphenol or aliphatic alcohol with twelve or more ethylene oxideunits and the oil-soluble calcium salt of dodecylbenzenesulfonic acid. Arange of hydrophile-lipophile balance (“HLB”) values from 8 to 18 willnormally provide good stable emulsions. Emulsion stability can sometimesbe improved by the addition of a small amount of an EO-PO blockcopolymer surfactant.

A solubilizing agent is a surfactant which will form micelles in waterat concentrations above the critical micelle concentration. The micellesare then able to dissolve or solubilize water-insoluble materials insidethe hydrophobic part of the micelle. The types of surfactants usuallyused for solubilization are non-ionics, sorbitan monooleates, sorbitanmonooleate ethoxylates, and methyl oleate esters.

Surfactants are sometimes used, either alone or with other additivessuch as mineral or vegetable oils as adjuvants to spray-tank mixes toimprove the biological performance of the pesticide on the target. Thetypes of surfactants used for bioenhancement depend generally on thenature and mode of action of the pesticide. However, they are oftennon-ionics such as: alkyl ethoxylates; linear aliphatic alcoholethoxylates; aliphatic amine ethoxylates.

A carrier or diluent in an agricultural formulation is a material addedto the pesticide to give a product of the required strength. Carriersare usually materials with high absorptive capacities, while diluentsare usually materials with low absorptive capacities. Carriers anddiluents are used in the formulation of dusts, wettable powders,granules and water-dispersible granules.

Organic solvents are used mainly in the formulation of emulsifiableconcentrates, oil-in-water emulsions, suspoemulsions, and ultra lowvolume formulations, and to a lesser extent, granular formulations.Sometimes mixtures of solvents are used. The first main groups ofsolvents are aliphatic paraffinic oils such as kerosene or refinedparaffins. The second main group (and the most common) comprises thearomatic solvents such as xylene and higher molecular weight fractionsof C9 and C10 aromatic solvents. Chlorinated hydrocarbons are useful ascosolvents to prevent crystallization of pesticides when the formulationis emulsified into water. Alcohols are sometimes used as cosolvents toincrease solvent power. Other solvents may include vegetable oils, seedoils, and esters of vegetable and seed oils.

Thickeners or gelling agents are used mainly in the formulation ofsuspension concentrates, emulsions and suspoemulsions to modify therheology or flow properties of the liquid and to prevent separation andsettling of the dispersed particles or droplets. Thickening, gelling,and anti-settling agents generally fall into two categories, namelywater-insoluble particulates and water-soluble polymers. It is possibleto produce suspension concentrate formulations using clays and silicas.Examples of these types of materials, include, but are not limited to,montmorillonite, bentonite, magnesium aluminum silicate, andattapulgite. Water-soluble polysaccharides have been used asthickening-gelling agents for many years. The types of polysaccharidesmost commonly used are natural extracts of seeds and seaweeds or aresynthetic derivatives of cellulose. Examples of these types of materialsinclude, but are not limited to, guar gum; locust bean gum; carrageenam;alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC);hydroxyethyl cellulose (HEC). Other types of anti-settling agents arebased on modified starches, polyacrylates, polyvinyl alcohol andpolyethylene oxide. Another good anti-settling agent is xanthan gum.

Microorganisms can cause spoilage of formulated products. Thereforepreservation agents are used to eliminate or reduce their effect.Examples of such agents include, but are not limited to: propionic acidand its sodium salt; sorbic acid and its sodium or potassium salts;benzoic acid and its sodium salt; p-hydroxybenzoic acid sodium salt;methyl p-hydroxybenzoate; and 1,2-benzisothiazolin-3-one (BIT).

The presence of surfactants often causes water-based formulations tofoam during mixing operations in production and in application through aspray tank. In order to reduce the tendency to foam, anti-foam agentsare often added either during the production stage or before fillinginto bottles. Generally, there are two types of anti-foam agents, namelysilicones and non-silicones. Silicones are usually aqueous emulsions ofdimethyl polysiloxane, while the non-silicone anti-foam agents arewater-insoluble oils, such as octanol and nonanol, or silica. In bothcases, the function of the anti-foam agent is to displace the surfactantfrom the air-water interface.

“Green” agents (e.g., adjuvants, surfactants, solvents) can reduce theoverall environmental footprint of crop protection formulations. Greenagents are biodegradable and generally derived from natural and/orsustainable sources, e.g. plant and animal sources. Specific examplesare: vegetable oils, seed oils, and esters thereof, also alkoxylatedalkyl polyglucosides.

For further information, see “Chemistry and Technology of AgrochemicalFormulations” edited by D. A. Knowles, copyright 1998 by Kluwer AcademicPublishers. Also see “Insecticides in Agriculture andEnvironment—Retrospects and Prospects” by A. S. Perry, I. Yamamoto, I.Ishaaya, and R. Perry, copyright 1998 by Springer-Verlag.

Pests

In general, the Molecules of Formula Formulas One, Two and Three may beused to control pests e.g. beetles, earwigs, cockroaches, flies. aphids,scales, whiteflies, leafhoppers, ants, wasps, termites, moths,butterflies, lice, grasshoppers, locusts, crickets, fleas, thrips,bristletails, mites, ticks, nematodes, and symphylans.

In another embodiment, the Molecules of Formulas One, Two and Three maybe used to control pests in the Phyla Nematoda and/or Arthropoda.

In another embodiment, the Molecules of Formulas One, Two and Three maybe used to control pests in the Subphyla Chelicerata, Myriapoda, and/orHexapoda.

In another embodiment, the Molecules of Formulas One, Two and Three maybe used to control pests in the Classes of Arachnida, Symphyla, and/orInsecta.

In another embodiment, the Molecules of Formulas One, Two and Three maybe used to control pests of the Order Anoplura. A non-exhaustive list ofparticular genera includes, but is not limited to, Haematopinus spp.,Hoplopleura spp., Linognathus spp., Pediculus spp., and Polyplax spp. Anon-exhaustive list of particular species includes, but is not limitedto, Haematopinus asini, Haematopinus suis, Linognathus setosus,Linognathus ovillus, Pediculus humanus capitis, Pediculus humanushumanus, and Pthirus pubis.

In another embodiment, the Molecules of Formulas One, Two and Three maybe used to control pests in the Order Coleoptera. A non-exhaustive listof particular genera includes, but is not limited to, Acanthoscelidesspp., Agriotes spp., Anthonomus spp., Apion spp., Apogonia spp.,Aulacophora spp., Bruchus spp., Cerosterna spp., Cerotoma spp.,Ceutorhynchus spp., Chaetocnema spp., Colaspis spp., Ctenicera spp.,Curculio spp., Cyclocephala spp., Diabrotica spp., Hypera spp., Ipsspp., Lyctus spp., Megascelis spp., Meligethes spp., Otiorhynchus spp.,Pantomorus spp., Phyllophaga spp., Phyllotreta spp., Rhizotrogus spp.,Rhynchites spp., Rhynchophorus spp., Scolytus spp., Sphenophorus spp.,Sitophilus spp., and Tribolium spp. A non-exhaustive list of particularspecies includes, but is not limited to, Acanthoscelides obtectus,Agrilus planipennis, Anoplophora glabripennis, Anthonomus grandis,Ataenius spretulus, Atomaria linearis, Bothynoderes punctiventris,Bruchus pisorum, Callosobruchus maculatus, Carpophilus hemipterus,Cassida vittata, Cerotoma trifurcata, Ceutorhynchus assimilis,Ceutorhynchus napi, Conoderus scalaris, Conoderus stigmosus,Conotrachelus nenuphar, Cotinis nitida, Crioceris asparagi, Cryptolestesferrugineus, Cryptolestes pusillus, Cryptolestes turcicus,Cylindrocopturus adspersus, Deporaus marginatus, Dermestes lardarius,Dermestes maculatus, Epilachna varivestis, Faustinus cubae, Hylobiuspales, Hypera postica, Hypothenemus hampei, Lasioderma serricorne,Leptinotarsa decemlineata, Liogenys fuscus, Liogenys suturalis,Lissorhoptrus oryzophilus, Maecolaspis joliveti, Melanotus communis,Meligethes aeneus, Melolontha melolontha, Oberea brevis, Oberealinearis, Oryctes rhinoceros, Oryzaephilus mercator, Oryzaephilussurinamensis, Oulema melanopus, Oulema oryzae, Phyllophaga cuyabana,Popillia japonica, Prostephanus truncatus, Rhyzopertha dominica, Sitonalineatus, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais,Stegobium paniceum, Tribolium castaneum, Tribolium confusum, Trogodermavariabile, and Zabrus tenebrioides.

In another embodiment, the Molecules of Formulas One, Two and Three maybe used to control pests of the Order Dermaptera.

In another embodiment, the Molecules of Formulas One, Two and Three maybe used to control pests of the Order Blattaria. A non-exhaustive listof particular species includes, but is not limited to, Blattellagermanica, Blatta orientalis, Parcoblatta pennsylvanica, Periplanetaamericana, Periplaneta australasiae, Periplaneta brunnea, Periplanetafuliginosa, Pycnoscelus surinamensis, and Supella longipalpa.

In another embodiment, the Molecules of Formulas One, Two and Three maybe used to control pests of the Order Diptera. A non-exhaustive list ofparticular genera includes, but is not limited to, Aedes spp., Agromyzaspp., Anastrepha spp., Anopheles spp., Bactrocera spp., Ceratitis spp.,Chrysops spp., Cochliomyia spp., Contarinia spp., Culex spp., Dasineuraspp., Delia spp., Drosophila spp., Fannia spp., Hylemyia spp., Liriomyzaspp., Musca spp., Phorbia spp., Tabanus spp., and Tipula spp. Anon-exhaustive list of particular species includes, but is not limitedto, Agromyza frontella, Anastrepha suspensa, Anastrepha ludens,Anastrepha obliqa, Bactrocera cucurbitae, Bactrocera dorsalis,Bactrocera invadens, Bactrocera zonata, Ceratitis capitata, Dasineurabrassicae, Delia platura, Fannia canicularis, Fannia scalaris,Gasterophilus intestinalis, Gracillia perseae, Haematobia irritans,Hypoderma lineatum, Liriomyza brassicae, Melophagus ovinus, Muscaautumnalis, Musca domestica, Oestrus ovis, Oscinella frit, Pegomyabetae, Psila rosae, Rhagoletis cerasi, Rhagoletis pomonella, Rhagoletismendax, Sitodiplosis mosellana, and Stomoxys calcitrans.

In another embodiment, the Molecules of Formulas One, Two and Three maybe used to control pests of the Order Hemiptera. A non-exhaustive listof particular genera includes, but is not limited to, Adelges spp.,Aulacaspis spp., Aphrophora spp., Aphis spp., Bemisia spp., Ceroplastesspp., Chionaspis spp., Chrysomphalus spp., Coccus spp., Empoasca spp.,Lepidosaphes spp., Lagynotomus spp., Lygus spp., Macrosiphum spp.,Nephotettix spp., Nezara spp., Philaenus spp., Phytocoris spp.,Piezodorus spp., Planococcus spp., Pseudococcus spp., Rhopalosiphumspp., Saissetia spp., Therioaphis spp., Toumeyella spp., Toxoptera spp.,Trialeurodes spp., Triatoma spp. and Unaspis spp. A non-exhaustive listof particular species includes, but is not limited to, Acrosternumhilare, Acyrthosiphon pisum, Aleyrodes proletella, Aleurodicusdispersus, Aleurothrixus floccosus, Amrasca biguttula biguttula,Aonidiella aurantii, Aphis gossypii, Aphis glycines, Aphis pomi,Aulacorthum solani, Bemisia argentifolii, Bemisia tabaci, Blissusleucopterus, Brachycorynella asparagi, Brevennia rehi, Brevicorynebrassicae, Calocoris norvegicus, Ceroplastes rubens, Cimex hemipterus,Cimex lectularius, Dagbertus fasciatus, Dichelops furcatus, Diuraphisnoxia, Diaphorina citri, Dysaphis plantaginea, Dysdercus suturellus,Edessa meditabunda, Eriosoma lanigerum, Eurygaster maura, Euschistusheros, Euschistus servus, Helopeltis antonii, Helopeltis theivora,Icerya purchasi, Idioscopus nitidulus, Laodelphax striatellus,Leptocorisa oratorius, Leptocorisa varicornis, Lygus hesperus,Maconellicoccus hirsutus, Macrosiphum euphorbiae, Macrosiphum granarium,Macrosiphum rosae, Macrosteles quadrilineatus, Mahanarva frimbiolata,Metopolophium dirhodum, Mictis longicornis, Myzus persicae, Nephotettixcinctipes, Neurocolpus longirostris, Nezara viridula, Nilaparvatalugens, Parlatoria pergandii, Parlatoria ziziphi, Peregrinus maidis,Phylloxera vitifoliae, Physokermes piceae, Phytocoris californicus,Phytocoris relativus, Piezodorus guildinii, Poecilocapsus lineatus,Psallus vaccinicola, Pseudacysta perseae, Pseudococcus brevipes,Quadraspidiotus perniciosus, Rhopalosiphum maidis, Rhopalosiphum padi,Saissetia oleae, Scaptocoris castanea, Schizaphis graminum, Sitobionavenae, Sogatella furcifera, Trialeurodes vaporariorum, Trialeurodesabutiloneus, Unaspis yanonensis, and Zulia entrerriana.

In another embodiment, the Molecules of Formulas One, Two and Three maybe used to control pests of the Order Hymenoptera. A non-exhaustive listof particular genera includes, but is not limited to, Acromyrmex spp.,Atta spp., Camponotus spp., Diprion spp., Formica spp., Monomorium spp.,Neodiprion spp., Pogonomyrmex spp., Polistes spp., Solenopsis spp.,Vespula spp., and Xylocopa spp. A non-exhaustive list of particularspecies includes, but is not limited to, Athalia rosae, Atta texana,Iridomyrmex humilis, Monomorium minimum, Monomorium pharaonis,Solenopsis invicta, Solenopsis geminata, Solenopsis molesta, Solenopsisrichtery, Solenopsis xyloni, and Tapinoma sessile.

In another embodiment, the Molecules of Formulas One, Two and Three maybe used to control pests of the Order Isoptera. A non-exhaustive list ofparticular genera includes, but is not limited to, Coptotermes spp.,Cornitermes spp., Cryptotermes spp., Heterotermes spp., Kalotermes spp.,Incisitermes spp., Macrotermes spp., Marginitermes spp., Microcerotermesspp., Procornitermes spp., Reticulitermes spp., Schedorhinotermes spp.,and Zootermopsis spp. A non-exhaustive list of particular speciesincludes, but is not limited to, Coptotermes curvignathus, Coptotermesfrenchi, Coptotermes formosanus, Heterotermes aureus, Microtermes obesi,Reticulitermes banyulensis, Reticulitermes grassei, Reticulitermesflavipes, Reticulitermes hageni, Reticulitermes hesperus, Reticulitermessantonensis, Reticulitermes speratus, Reticulitermes tibialis, andReticulitermes virginicus.

In another embodiment, the Molecules of Formulas One, Two and Three maybe used to control pests of the Order Lepidoptera. A non-exhaustive listof particular genera includes, but is not limited to, Adoxophyes spp.,Agrotis spp., Argyrotaenia spp., Cacoecia spp., Caloptilia spp., Chilospp., Chrysodeixis spp., Colias spp., Crambus spp., Diaphania spp.,Diatraea spp., Earias spp., Ephestia spp., Epimecis spp., Feltia spp.,Gortyna spp., Helicoverpa spp., Heliothis spp., Indarbela spp.,Lithocolletis spp., Loxagrotis spp., Malacosoma spp., Peridroma spp.,Phyllonorycter spp., Pseudaletia spp., Sesamia spp., Spodoptera spp.,Synanthedon spp., and Yponomeuta spp. A non-exhaustive list ofparticular species includes, but is not limited to, Achaea janata,Adoxophyes orana, Agrotis ipsilon, Alabama argillacea, Amorbia cuneana,Amyelois transitella, Anacamptodes defectaria, Anarsia lineatella,Anomis sabulifera, Anticarsia gemmatalis, Archips argyrospila, Archipsrosana, Argyrotaenia citrana, Autographa gamma, Bonagota cranaodes,Borbo cinnara, Bucculatrix thurberiella, Capua reticulana, Carposinaniponensis, Chlumetia transversa, Choristoneura rosaceana,Cnaphalocrocis medinalis, Conopomorpha cramerella, Cossus cossus, Cydiacaryana, Cydia funebrana, Cydia molesta, Cydia nigricana, Cydiapomonella, Darna diducta, Diatraea saccharalis, Diatraea grandiosella,Earias insulana, Earias vittella, Ecdytolopha aurantianum, Elasmopalpuslignosellus, Ephestia cautella, Ephestia elutella, Ephestia kuehniella,Epinotia aporema, Epiphyas postvittana, Erionota thrax, Eupoeciliaambiguella, Euxoa auxiliaris, Grapholita molesta, Hedylepta indicata,Helicoverpa armigera, Helicoverpa zea, Heliothis virescens, Hellulaundalis, Keiferia lycopersicella, Leucinodes orbonalis, Leucopteracoffeella, Leucoptera malifoliella, Lobesia botrana, Loxagrotisalbicosta, Lymantria dispar, Lyonetia clerkella, Mahasena corbetti,Mamestra brassicae, Maruca testulalis, Metisa plana, Mythimna unipuncta,Neoleucinodes elegantalis, Nymphula depunctalis, Operophtera brumata,Ostrinia nubilalis, Oxydia vesulia, Pandemis cerasana, Pandemisheparana, Papilio demodocus, Pectinophora gossypiella, Peridroma saucia,Perileucoptera coffeella, Phthorimaea operculella, Phyllocnistiscitrella, Pieris rapae, Plathypena scabra, Plodia interpunctella,Plutella xylostella, Polychrosis viteana, Prays endocarpa, Prays oleae,Pseudaletia unipuncta, Pseudoplusia includens, Rachiplusia nu,Scirpophaga incertulas, Sesamia inferens, Sesamia nonagrioides, Setoranitens, Sitotroga cerealella, Sparganothis pilleriana, Spodopteraexigua, Spodoptera frugiperda, Spodoptera eridania, Thecla basilides,Tineola bisselliella, Trichoplusia ni, Tuta absoluta, Zeuzera coffeae,and Zeuzera pyrina.

In another embodiment, the Molecules of Formulas One, Two and Three maybe used to control pests of the Order Mallophaga. A non-exhaustive listof particular genera includes, but is not limited to, Anaticola spp.,Bovicola spp., Chelopistes spp., Goniodes spp., Menacanthus spp., andTrichodectes spp. A non-exhaustive list of particular species includes,but is not limited to, Bovicola bovis, Bovicola caprae, Bovicola ovis,Chelopistes meleagridis, Goniodes dissimilis, Goniodes gigas,Menacanthus stramineus, Menopon gallinae, and Trichodectes canis.

In another embodiment, the Molecules of Formulas One, Two and Three maybe used to control pests of the Order Orthoptera. A non-exhaustive listof particular genera includes, but is not limited to, Melanoplus spp.,and Pterophylla spp. A non-exhaustive list of particular speciesincludes, but is not limited to, Anabrus simplex, Gryllotalpa africana,Gryllotalpa australis, Gryllotalpa brachyptera, Gryllotalpa hexadactyla,Locusta migratoria, Microcentrum retinerve, Schistocerca gregaria, andScudderia furcata.

In another embodiment, the Molecules of Formulas One, Two and Three maybe used to control pests of the Order Siphonaptera. A non-exhaustivelist of particular species includes, but is not limited to,Ceratophyllus gallinae, Ceratophyllus niger, Ctenocephalides canis,Ctenocephalides felis, and Pulex irritans.

In another embodiment, the Molecules of Formulas One, Two and Three maybe used to control pests of the Order Thysanoptera. A non-exhaustivelist of particular genera includes, but is not limited to, Caliothripsspp., Frankliniella spp., Scirtothrips spp., and Thrips spp. Anon-exhaustive list of particular sp. includes, but is not limited to,Frankliniella fusca, Frankliniella occidentalis, Frankliniellaschultzei, Frankliniella williamsi, Heliothrips haemorrhoidalis,Rhipiphorothrips cruentatus, Scirtothrips citri, Scirtothrips dorsalis,and Taeniothrips rhopalantennalis, Thrips hawaiiensis, Thripsnigropilosus, Thrips orientalis, Thrips tabaci.

In another embodiment, the Molecules of Formulas One, Two and Three maybe used to control pests of the Order Thysanura. A non-exhaustive listof particular genera includes, but is not limited to, Lepisma spp. andThermobia spp.

In another embodiment, the Molecules of Formulas One, Two and Three maybe used to control pests of the Order Acarina. A non-exhaustive list ofparticular genera includes, but is not limited to, Acarus spp., Aculopsspp., Boophilus spp., Demodex spp., Dermacentor spp., Epitrimerus spp.,Eriophyes spp., Ixodes spp., Oligonychus spp., Panonychus spp.,Rhizoglyphus spp., and Tetranychus spp. A non-exhaustive list ofparticular species includes, but is not limited to, Acarapis woodi,Acarus siro, Aceria mangiferae, Aculops lycopersici, Aculus pelekassi,Aculus schlechtendali, Amblyomma americanum, Brevipalpus obovatus,Brevipalpus phoenicis, Dermacentor variabilis, Dermatophagoidespteronyssinus, Eotetranychus carpini, Notoedres cati, Oligonychuscoffeae, Oligonychus ilicis, Panonychus citri, Panonychus ulmi,Phyllocoptruta oleivora, Polyphagotarsonemus latus, Rhipicephalussanguineus, Sarcoptes scabiei, Tegolophus perseaflorae, Tetranychusurticae, and Varroa destructor.

In another embodiment, the Molecules of Formulas One, Two and Three maybe used to control pest of the Order Symphyla. A non-exhaustive list ofparticular sp. includes, but is not limited to, Scutigerella immaculata.

In another embodiment, the Molecules of Formulas One, Two and Three maybe used to control pests of the Phylum Nematoda. A non-exhaustive listof particular genera includes, but is not limited to, Aphelenchoidesspp., Belonolaimus spp., Criconemella spp., Ditylenchus spp., Heteroderaspp., Hirschmanniella spp., Hoplolaimus spp., Meloidogyne spp.,Pratylenchus spp., and Radopholus spp. A non-exhaustive list ofparticular sp. includes, but is not limited to, Dirofilaria immitis,Heterodera zeae, Meloidogyne incognita, Meloidogyne javanica, Onchocercavolvulus, Radopholus similis, and Rotylenchulus reniformis.

For additional information consult “HANDBOOK OF PEST CONTROL—THEBEHAVIOR, LIFE HISTORY, AND CONTROL OF HOUSEHOLD PESTS” by ArnoldMallis, 9th Edition, copyright 2004 by GIE Media Inc.

Applications

Molecules of Formulas One, Two and Three are generally used in amountsfrom about 0.01 grams per hectare to about 5000 grams per hectare toprovide control. Amounts from about 0.1 grams per hectare to about 500grams per hectare are generally preferred, and amounts from about 1 gramper hectare to about 50 grams per hectare are generally more preferred.

The area to which a molecule of Formulas One, Two and Three is appliedcan be any area inhabited (or maybe inhabited, or traversed by) a pest,for example: where crops, trees, fruits, cereals, fodder species, vines,turf and ornamental plants, are growing; where domesticated animals areresiding; the interior or exterior surfaces of buildings (such as placeswhere grains are stored), the materials of construction used in building(such as impregnated wood), and the soil around buildings. Particularcrop areas to use a molecule of Formula One include areas where apples,corn, sunflowers, cotton, soybeans, canola, wheat, rice, sorghum,barley, oats, potatoes, oranges, alfalfa, lettuce, strawberries,tomatoes, peppers, crucifers, pears, tobacco, almonds, sugar beets,beans and other valuable crops are growing or the seeds thereof aregoing to be planted. It is also advantageous to use aluminum sulfatewith a molecule of Formula One when growing various plants.

Controlling pests generally means that pest populations, pest activity,or both, are reduced in an area. This can come about when: pestpopulations are repulsed from an area; when pests are incapacitated inor around an area; or pests are exterminated, in whole, or in part, inor around an area. Of course, a combination of these results can occur.Generally, pest populations, activity, or both are desirably reducedmore than fifty percent, preferably more than 90 percent. Generally, thearea is not in or on a human; consequently, the locus is generally anon-human area.

The Molecules of Formulas One, Two and Three may be used in mixtures,applied simultaneously or sequentially, alone or with other compounds toenhance plant vigor (e.g. to grow a better root system, to betterwithstand stressful growing conditions). Such other compounds are, forexample, compounds that modulate plant ethylene receptors, most notably1-methylcyclopropene (also known as 1-MCP).

The Molecules of Formulas One, Two and Three can be applied to thefoliar and fruiting portions of plants to control pests. The moleculeswill either come in direct contact with the pest, or the pest willconsume the pesticide when eating leaf, fruit mass, or extracting sap,that contains the pesticide. The Molecules of Formulas One, Two andThree can also be applied to the soil, and when applied in this manner,root and stem feeding pests can be controlled. The roots can absorb amolecule taking it up into the foliar portions of the plant to controlabove ground chewing and sap feeding pests.

Generally, with baits, the baits are placed in the ground where, forexample, termites can come into contact with, and/or be attracted to,the bait. Baits can also be applied to a surface of a building,(horizontal, vertical, or slant surface) where, for example, ants,termites, cockroaches, and flies, can come into contact with, and/or beattracted to, the bait. Baits can comprise a molecule of Formula One,Two or Three.

The Molecules of Formulas One, Two and Three can be encapsulated inside,or placed on the surface of a capsule. The size of the capsules canrange from nanometer size (about 100-900 nanometers in diameter) tomicrometer size (about 10-900 microns in diameter).

Because of the unique ability of the eggs of some pests to resistcertain pesticides, repeated applications of the Formula One, Two orThree may be desirable to control newly emerged larvae.

Systemic movement of pesticides in plants may be utilized to controlpests on one portion of the plant by applying (for example by sprayingan area) the Molecules of Formula One, Two or Three to a differentportion of the plant. For example, control of foliar-feeding insects canbe achieved by drip irrigation or furrow application, by treating thesoil with for example pre- or post-planting soil drench, or by treatingthe seeds of a plant before planting.

Seed treatment can be applied to all types of seeds, including thosefrom which plants genetically modified to express specialized traitswill germinate. Representative examples include those expressingproteins toxic to invertebrate pests, such as Bacillus thuringiensis orother insecticidal toxins, those expressing herbicide resistance, suchas “Roundup Ready” seed, or those with “stacked” foreign genesexpressing insecticidal toxins, herbicide resistance,nutrition-enhancement, drought resistance, or any other beneficialtraits. Furthermore, such seed treatments with the Molecules of FormulaOne, Two or Three may further enhance the ability of a plant to betterwithstand stressful growing conditions. This results in a healthier,more vigorous plant, which can lead to higher yields at harvest time.Generally, about 1 gram of the Molecules of Formula One, Two or Three toabout 500 grams per 100,000 seeds is expected to provide good benefits,amounts from about 10 grams to about 100 grams per 100,000 seeds isexpected to provide better benefits, and amounts from about 25 grams toabout 75 grams per 100,000 seeds is expected to provide even betterbenefits.

It should be readily apparent that the Molecules of Formulas One, Twoand Three may be used on, in, or around plants genetically modified toexpress specialized traits, such as Bacillus thuringiensis or otherinsecticidal toxins, or those expressing herbicide resistance, or thosewith “stacked” foreign genes expressing insecticidal toxins, herbicideresistance, nutrition-enhancement, or any other beneficial traits.

The Molecules of Formulas One, Two and Three may be used for controllingendoparasites and ectoparasites in the veterinary medicine sector or inthe field of non-human animal keeping. The Molecules of Formulas One,Two and Three are applied, such as by oral administration in the formof, for example, tablets, capsules, drinks, granules, by dermalapplication in the form of, for example, dipping, spraying, pouring on,spotting on, and dusting, and by parenteral administration in the formof, for example, an injection.

The Molecules of Formulas One, Two and Three may also be employedadvantageously in livestock keeping, for example, cattle, sheep, pigs,chickens, and geese. They may also be employed advantageously in petssuch as, horses, dogs, and cats. Particular pests to control would befleas and ticks that are bothersome to such animals. Suitableformulations are administered orally to the animals with the drinkingwater or feed. The dosages and formulations that are suitable depend onthe species.

The Molecules of Formulas One, Two and Three may also be used forcontrolling parasitic worms, especially of the intestine, in the animalslisted above.

The Molecules of Formula One, Two, and Three may also be employed intherapeutic methods for human health care. Such methods include, but arelimited to, oral administration in the form of, for example, tablets,capsules, drinks, granules, and by dermal application.

Pests around the world have been migrating to new environments (for suchpest) and thereafter becoming a new invasive species in such newenvironment. The Molecules of Formula One and Two may also be used onsuch new invasive species to control them in such new environment.

The Molecules of Formula One, Two, and Three may also be used in an areawhere plants, such as crops, are growing (e.g. pre-planting, planting,pre-harvesting) and where there are low levels (even no actual presence)of pests that can commercially damage such plants. The use of suchmolecules in such area is to benefit the plants being grown in the area.Such benefits, may include, but are not limited to, improving the healthof a plant, improving the yield of a plant (e.g. increased biomassand/or increased content of valuable ingredients), improving the vigorof a plant (e.g. improved plant growth and/or greener leaves), improvingthe quality of a plant (e.g. improved content or composition of certainingredients), and improving the tolerance to abiotic and/or bioticstress of the plant.

Before a pesticide can be used or sold commercially, such pesticideundergoes lengthy evaluation processes by various governmentalauthorities (local, regional, state, national, and international).Voluminous data requirements are specified by regulatory authorities andmust be addressed through data generation and submission by the productregistrant or by a third party on the product registrant's behalf, oftenusing a computer with a connection to the World Wide Web. Thesegovernmental authorities then review such data and if a determination ofsafety is concluded, provide the potential user or seller with productregistration approval. Thereafter, in that locality where the productregistration is granted and supported, such user or seller may use orsell such pesticide.

A molecule according to Formula One, Two, and Three can be tested todetermine its efficacy against pests. Furthermore, mode of actionstudies can be conducted to determine if said molecule has a differentmode of action than other pesticides. Thereafter, such acquired data canbe disseminated, such as by the internet, to third parties.

The headings in this document are for convenience only and must not beused to interpret any portion hereof.

Table Section

BAW & CEW Rating Table % Control (or Mortality) Rating 50-100 A Morethan 0-Less than 50 B Not Tested C No activity noticed in this bioassayD

GPA Rating Table % Control (or Mortality) Rating 80-100 A More than0-Less than 80 B Not Tested C No activity noticed in this bioassay D

TABLE 1 Structures for Compounds ID Structures I-4 

I-5 

I-6 

I-7 

I-8 

I-9 

I-10

I-11

I-12

I-13

I-14

I-15

I-16

I-17

I-18

I-19

I-20

I-21

I-22

I-23

I-24

I-25

I-26

I-27

I-28

I-29

I-30

I-31

I-32

I-33

I-34

I-35

I-36

I-37

I-38

I-39

I-40

I-41

I-42

I-43

I-44

I-45

I-46

I-47

I-48

I-49

I-50

I-51

I-52

I-53

I-54

I-55

I-56

I-57

I-58

I-59

I-60

I-61

I-62

TABLE 2 Analytical Data for Compounds in Table 1. Synthesis ¹H, ¹³C, or¹⁹F NMR ID Method MS mp (° C.) (δ)¹ I-4 A 551 (M + 1) 209-211 (DMSO-d₆)12.06 (s, 1H), 10.19 (s, 1H), 9.42 (s, 1H), 8.22 (s, 1H), 8.17-8.03 (m,5H), 7.66-7.57 (m, 4H), 7.42-7.38 (m, 2H) I-5 C 511 (M + 1) 220-225(CDCl₃) 9.30 (s, 1H), 8.69 (s, 1H), 8.60 (s, 1H), 8.26 (d, J = 8.4 Hz,2H), 7.89 (s, 1H), 7.81 (m, 4H), 7.41 (d, J = 8.4 Hz, 2H), 7.19 (m, 3H),2.35 (s, 6H) I-6 C 555 (M + H) 206-209 (CDCl₃) 8.90 (s, 1H), 8.80 (s,1H), 8.6 (s, 1H), 8.28 (d, J = 8.4 Hz, 2H), 8.9-8.7 (m, 4H), 7.4 (d, J =8.6 Hz, 2H), 6.7 (s, 2H), 3.80 (s, 3H), 2.39 (s, 3H), 2.32 (s, 6H) I-7 C541 (M + H) 202-210 (CDCl₃) 9.88 (s, 1H), 8.61 (s, 1H), 8.60 (s, 1H),8.27 (d, J = 8.4 Hz, 2H), 7.9 (s, 1H), 7.9-7.7 (m, 4H), 7.4 (d, J = 8.6Hz, 2H), 6.7 (s, 2H), 3.81 (s, 3H), 2.33 (s, 6H) I-8 B 581 195-199(CDCl₃) 10.2 (s, 1H), 8.7 (s, 1H), 8.6 (s, 1H), 8.25 (d, J = 8.4 Hz,2H), 8.0 (s, 1H), 7.82 (m, 4H), 7.4 (d, J = 8.4 Hz, 2H), 7.0 (s, 2H),3.82 (s, 3H) I-9 C 591 (M + H) 233-236 (CDCl₃) 9.89 (s, 1H), 8.60 (s,2H), 8.25 (d, J = 8.5 Hz, 2H), 7.95 (s, 1H), 7.88-7.70 (m, 4H), 7.41 (d,J = 9.0 Hz, 2H), 6.70 (s, 2H), 3.81 (s, 3H), 2.31 (s, 6H) I-10 C 525(M + H) 230-240 (CDCl₃) 9.93 (s, 1H), 8.69 (s, 1H), 8.60 (s, 1H), 8.26(d, J = 8.4 Hz, 2H), 7.93 (d, J = 9.5 Hz, 2H), 7.95 (s, 1H), 7.86-7.75(m, 4H), 6.69 (s, 2H), 3.81 (s, 3H), 2.31 (s, 6H) I-11 C 561 (M + H)234-238 (CDCl₃) 9.62 (s, 1H), 8.70 (s, 1H), 8.60 (s, 1H), 8.26 (d, J =8.4 Hz, 2H), 7.92 (s, 1H), 7.86-7.75 (m, 4H), 7.41 (d, J = 9.0 Hz, 2H),7.18 (m, 3H), 2.35 (s, 6H) I-12 C 577 (M + H) 197-200 (CDCl₃) 10.2 (s,1H), 8.90 (s, 1H), 8.62 (s, 1H), 8.25 (d, J = 8.4 Hz, 2H), 7.98 (s, 1H),7.9-7.7 (m, 4H), 7.4 (m, 3H), 6.8 (m, 2H), 3.82 (s, 3H), 2.37 (s, 3H)I-13 B 541 (M + H) 180-186 (CDCl₃) 9.9 (s, 1H), 8.6 (s, 1H), 8.23 (d, J= 8.4 Hz, 2H), 7.9 (s, 1H), 7.8 (d, J = 8.6 Hz, 2H), 7.75 (d, J = 8.4Hz, 2H), 7.7 (d, J = 7 Hz, 1H), 7.45-7.35 (m, 4H), 6.91 (d, J = 8 Hz,2H), 5.73 (m, 1H), 3.80 (s, 3H), 1.65 (d, J = 7.2 Hz, 3H) I-14 B 559(M + H) 196-203 (CDCl₃) 9.32 (s, 1H), 8.6 (s, 1H), 8.22 (d, J = 8.4 Hz,2H), 7.85-7.7 (m, 5H), 7.6 (d, J = 6 Hz, 1H), 7.4 (d, J = 8.5 Hz, 2H),7.25-7.15 (m, 2H), 6.93 (m, 1H), 5.7 (m, 1H), 3.89 (s, 3H), 1.67 (d, J =6 Hz, 3H) I-15 B 511 (M + H) 201-206 (CDCl₃) 9.32 (s, 1H), 8.61 (s, 1H),8.27 (d, J = 8.4 Hz, 2H), 7.9-7.7 (m, 6H), 7.5-7.3 (m, 7H), 5.76 (m,1H), 1.67 (d, J = 7 Hz, 3H) I-16 C 525 (M + 1) 218-225 (CDCl₃) 9.37 (s,1H), 8.63 (s, 1H), 8.60 (s, 1H), 8.26 (d, J = 8.4 Hz, 2H), 7.89 (s, 1H),7.85-7.76 (m, 4H), 7.41 (d, J = 8.4 Hz, 2H), 6.97 (s, 2H), 2.32 (s, 3H),2.30 (s, 6H) I-17 C 525 (M + H) 168-180 (CDCl₃) 10.2 (s, 1H), 9.07 (s,1H), 8.63 (s, 1H), 8.25 (d, J = 8.4 Hz, 2H), 8.0 (s, 1H), 7.9-7.7 (m,4H), 7.65 (d, J = 8 Hz, 1H), 7.4-7.25 (m, 5H), 3.25 (heptet, J = 7 Hz,1H), 1.35 (d, J = 7 Hz, 6H) I-18 C 539 (M + 1) 216-221 (CDCl₃) δ 9.29(s, 1H), 8.87 (s, 1H), 8.59 (s, 1H), 8.31-8.19 (m, 2H), 7.90-7.84 (m,2H), 7.85-7.79 (m, 2H), 7.73 (dd, J = 7.5, 1.7 Hz, 1H), 7.39 (dd, J =12.6, 5.1 Hz, 3H), 7.35-7.27 (m, 2H), 3.37-3.04 (m, 1H), 2.40 (s, 3H),1.29 (d, J = 7.5 Hz, 6H) I-19 C 509 (M + 1) 223-225 (CDCl₃) δ 9.74 (s,1H), 9.06 (s, 1H), 8.69 (s, 1H), 8.31-8.20 (m, 2H), 7.98-7.84 (m, 3H),7.80 (m, 4H), 7.65 (d, J = 1.4 Hz, 1H), 7.43-7.28 (m, 3H), 3.19 (heptet,J = 6.9 Hz, 1H), 1.32 (d, J = 6.9 Hz, 6H) I-20 C 538 (M + H) 220 (dec)(CDCl₃) δ 9.52 (s, 1H), 9.31 (s, 1H), 8.66 (d, J = 8.2 Hz, 1H), 8.60 (s,1H), 8.25 (d, J = 8.4 Hz, 2H), 7.87 (s, 1H), 7.86-7.80 (m, 2H), 7.77 (d,J = 8.4 Hz, 2H), 7.41 (d, J = 8.3 Hz, 2H), 7.32 (ddd, J = 13.9, 7.2, 4.3Hz, 1H), 7.24-7.15 (m, 2H), 6.27 (s, 1H), 2.03 (d, J = 1.3 Hz, 3H), 1.73(d, J = 1.1 Hz, 3H) I-21 C 540 (M + H) 207-210; (CDCl₃) δ 9.48 (s, 1H),9.14 (s, 1H), 215-218 8.60 (s, 1H), 8.26 (d, J = 8.4 Hz, 2H), 7.92 (s,1H), 7.87 (d, J = 7.7 Hz, 1H), 7.84-7.76 (m, 4H), 7.40 (d, J = 8.3 Hz,2H), 7.30 (dt, J = 8.2, 3.7 Hz, 1H), 7.28-7.23 (m, 2H), 2.57 (d, J = 7.2Hz, 2H), 1.93 (dq, J = 13.6, 6.7 Hz, 1H), 0.98 (d, J = 6.6 Hz, 6H) I-22C 540 (M + H) 210-215 (CDCl₃) δ 9.46 (s, 1H), 9.05 (s, 1H), 8.60 (s,1H), 8.26 (d, J = 8.4 Hz, 2H), 7.91 (s, 1H), 7.84-7.74 (m, 4H), 7.69 (d,J = 7.4 Hz, 1H), 7.40 (d, J = 8.3 Hz, 2H), 7.36-7.27 (m, 3H), 2.91 (dt,J = 13.9, 6.9 Hz, 1H), 1.75-1.58 (m, 2H), 1.30 (d, J = 6.9 Hz, 3H), 0.92(t, J = 7.4 Hz, 3H) I-23 C 560 (M + H) 213-216 (CDCl₃) δ 9.41 (s, 1H),9.01 (s, 1H), 8.74 (d, J = 7.7 Hz, 1H), 8.60 (s, 1H), 8.15 (d, J = 8.4Hz, 2H), 7.86-7.78 (m, 2H), 7.69 (s, 1H), 7.57-7.44 (m, 6H), 7.42 (d, J= 9.1 Hz, 2H), 7.37-7.27 (m, 4H) I-24 C 524 (M + H) 200-206; (CDCl₃) δ9.65 (d, J = 17.9 Hz, 1H), 210-211 9.20 (s, 1H), 8.60 (s, 1H), 8.27 (dd,J = 8.0, 4.5 Hz, 3H), 7.89 (s, 1H), 7.86-7.75 (m, 4H), 7.41 (d, J = 8.3Hz, 2H), 7.30-7.27 (m, 1H), 7.18 (q, J = 7.8 Hz, 2H), 2.00-1.90 (m, 1H),1.09-1.01 (m, 2H), 0.81-0.73 (m, 2H) I-25 C 550 (M + H) 221-223(DMSO-d₆) δ 12.13 (s, 1H), 10.07 (s, 1H), 9.44 (s, 1H), 8.23 (s, 1H),8.16 (d, J = 8.4 Hz, 2H), 8.13-8.06 (m, 2H), 8.01-7.98 (m, 3H), 7.63 (d,J = 8.4 Hz, 2H), 7.38-7.26 (m, 3H), 7.23 (t, J_(HF) = 74.1 Hz, 1H) I-26C 590 (M + H) 230-231 (CDCl₃) δ 9.37 (s, 1H), 8.60 (s, 1H), 8.57 (s,1H), 8.27 (d, J = 8.4 Hz, 2H), 7.90 (s, 1H), 7.81 (dt, J = 8.5, 4.8 Hz,4H), 7.41 (d, J = 8.3 Hz, 2H), 7.31 (s, 2H), 2.31 (s, 6H) I-27 C 556(M + H) 190-192 (CDCl₃) δ 9.39 (s, 1H), 9.15 (s, 1H), 8.61 (s, 1H), 8.29(d, J = 8.4 Hz, 2H), 8.16-8.05 (m, 2H), 7.95-7.85 (m, 3H), 7.85-7.76 (m,4H), 7.41 (d, J = 8.3 Hz, 2H), 4.39 (q, J = 7.1 Hz, 2H), 1.41 (t, J =7.1 Hz, 3H) I-28 C 528 (M + H) 219-221 (300 MHz, CDCl₃) δ 10.17 (s, 1H),9.09 (s, 1H), 9.03 (t, J = 5.4 Hz, 1H), 8.60 (s, 1H), 8.23 (t, J = 8.9Hz, 2H), 7.89-7.76 (m, 5H), 7.39 (t, J = 7.2 Hz, 2H), 7.17-7.07 (m, 1H),7.03 (d, J = 7.8 Hz, 1H), 6.94 (d, J = 6.9 Hz, 1H), 4.18 (q, J = 7.1 Hz,2H), 1.61 (t, J = 7.0 Hz, 3H) I-29 C 499 (M + 1) 195-200 (DMSO-d₆) δ9.44 (s, 1H), 8.49 (s, 1H), 8.42 (d, J = 5.2 Hz, 1H), 8.29-8.21 (m, 2H),8.16 (d, J = 8.5 Hz, 2H), 8.10 (d, J = 2.3 Hz, 1H), 8.08 (d, J = 3.0 Hz,1H), 8.04 (t, J = 6.5 Hz, 2H), 7.63 (d, J = 8.3 Hz, 3H), 2.29 (s, 3H)I-30 C 499 (M + 1) 114-118 (CDCl₃) δ 8.60 (s, 1H), 8.31 (s, 1H), 8.24(d, J = 8.4 Hz, 2H), 8.16 (d, J = 3.9 Hz, 1H), 7.95 (d, J = 8.4 Hz, 2H),7.82 (d, J = 9.0 Hz, 2H), 7.55 (d, J = 6.7 Hz, 1H), 7.41 (s, 2H), 6.99(dd, J = 7.4, 5.1 Hz, 1H), 2.35 (s, 3H). I-31 C 513 (M + 1) 122-125(CDCl₃) δ 8.60 (s, 1H), 8.32 (s, 1H), 8.25 (d, J = 8.4 Hz, 2H),8.19-8.16 (m, 1H), 7.97 (d, J = 8.4 Hz, 2H), 7.84-7.81 (m, 2H), 7.58 (d,J = 7.5 Hz, 1H), 7.40 (d, J = 8.3 Hz, 2H), 7.03 (dd, J = 7.5, 5.1 Hz,1H), 2.67 (s, 2H), 1.35 (t, J = 7.5 Hz, 3H) I-32 N 190 ([M + H]⁺) —(CDCl₃) δ 7.78-7.71 (m, 1H), 7.54-7.47 (m, 1H), 7.40-7.32 (m, 2H),5.86-5.82 (m, 1H), 2.63-2.55 (m, 2H), 2.55-2.47 (m, 2H), 2.09-1.98 (m,2H); ¹³C NMR (101 MHz, CDCl₃) δ 148.77, 139.96, 133.58, 132.08, 130.87,130.52, 127.55, 123.70, 35.31, 33.49, 24.05 I-33 N 162 ([M + H]⁺) —(CDCl₃) δ 7.14 (dd, J = 7.7, 1.3 Hz, 1H), 7.02 (td, J = 7.6, 1.5 Hz,1H), 6.76 (td, J = 7.4, 1.1 Hz, 1H), 6.68 (dd, J = 7.8, 1.2 Hz, 1H),3.66 (bs, 2H), 3.04-2.92 (m, 1H), 2.13-1.98 (m, 2H), 1.88-1.58 (m, 6H);¹³C NMR (101 MHz, CDCl₃) δ 144.12, 130.34, 126.51, 125.95, 118.78,115.70, 39.89, 32.17, 25.21 I-34 N 236 ([M + H]⁺) — CDCl₃) δ 9.02 (bs,1H), 7.52 (bs, 1H), 7.41-7.18 (m, 4H), 4.06 (bs, 2H), 3.21-3.06 (m, 1H),2.04 (s, 2H), 1.90-1.74 (m, 2H), 1.74-1.58 (m, 4H); I-35 C 551 ([M +H]⁺) 213-216 (CDCl₃) δ 9.45 (s, 1H), 9.11 (s, 1H), 8.60 (s, 1H), 8.26(d, J = 8.4 Hz, 2H), 7.91 (s, 1H), 7.86-7.71 (m, 5H), 7.40 (dd, J = 8.8,6.4 Hz, 3H), 7.35-7.27 (m, 2H), 3.22 (t, J = 8.0 Hz, 1H), 2.13 (d, J =2.5 Hz, 2H), 1.90-1.59 (m, 6H) I-36 N — — (CDCl₃) δ 7.48-7.36 (m, 1H),7.21-7.06 (m, 2H), 5.23 (p, J = 1.5 Hz, 1H), 5.05 (q, J = 1.1 Hz, 1H),2.09 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 153.56 (d, J_(CF) = 257.5 Hz),139.62, 139.60, 138.83, 131.48 (d, J_(CF) = 8.6 Hz), 124.47 (d, J_(CF) =3.6 Hz), 117.60, 115.51 (d, J_(CF) = 19.1 Hz), 23.18 I-37 N — — (CDCl₃)δ 6.92 (dt, J = 7.7, 1.2 Hz, 1H), 6.86 (ddd, J = 10.8, 8.1, 1.4 Hz, 1H),6.69 (td, J = 8.0, 5.6 Hz, 1H), 3.71 (bs, 2H), 2.92 (hept, J = 6.8 Hz,1H), 1.26 (d, J = 6.8 Hz, 6H); ¹³C NMR (101 MHz, CDCl₃) δ 151.91 (d, J =237.6 Hz), 135.10 (d, J = 2.3 Hz), 131.60 (d, J = 11.8 Hz), 120.52 (d, J= 3.0 Hz), 117.99 (d, J = 8.0 Hz), 112.28 (d, J = 19.6 Hz), 27.77 (d, J= 2.9 Hz), 22.22 I-38 N 229 ([M + H]⁺) 122-124 (CDCl₃) δ 8.56 (bs, 1H),7.54 (bs, 1H), 7.32 (td, J = 8.1, 5.6 Hz, 1H), 7.17-7.09 (m, 1H), 7.00(ddd, J = 9.5, 8.2, 1.4 Hz, 1H), 4.07 (bs, 2H), 3.15 (hept, J = 7.0 Hz,1H), 1.24 (d, J = 6.9 Hz, 6H), 7.78-7.39 (m, 1H) I-39 C 544 ([M + H]⁺)210-212 (CDCl₃) δ 9.54 (s, 1H), 8.60 (s, 1H), 8.56 (s, 1H), 8.30-8.22(m, 2H), 7.92 (s, 1H), 7.86-7.76 (m, 4H), 7.44-7.38 (m, 2H), 7.35 (dd, J= 8.1, 5.6 Hz, 1H), 7.18 (d, J = 7.9 Hz, 1H), 7.04 (ddd, J = 9.4, 8.2,1.3 Hz, 1H), 3.22 (p, J = 6.9 Hz, 1H), 1.29 (d, J = 6.9 Hz, 6H) I-40 N —— (CDCl₃) δ 7.60 (dd, J = 8.2, 2.5 Hz, 1H), 7.37-7.21 (m, 2H), 5.19 (p,J = 1.5 Hz, 1H), 4.97-4.89 (m, 1H), 2.11-2.04 (m, 3H); ¹³C NMR (101 MHz,CDCl₃) δ 160.96 (d, J = 250.8 Hz), 148.46, 141.88, 135.18 (d, J = 4.1Hz), 132.09 (d, J = 7.8 Hz), 119.98 (d, J = 20.9 Hz), 115.99, 111.63 (d,J = 26.4 Hz), 23.35 I-41 N — — (CDCl₃) δ 7.05 (dd, J = 8.5, 6.4 Hz, 1H),6.45 (td, J = 8.5, 2.6 Hz, 1H), 6.37 (dd, J = 10.6, 2.6 Hz, 1H), 3.74(bs, 2H), 2.83 (hept, J = 6.8 Hz, 1H), 1.24 (d, J = 6.8 Hz, 6H); ¹³C NMR(101 MHz, CDCl₃) δ 161.75 (d, J = 241.3 Hz), 144.76 (d, J = 10.3 Hz),128.11 (d, J = 2.8 Hz), 126.53 (d, J = 9.6 Hz), 105.06 (d, J = 20.7 Hz),102.26 (d, J = 24.2 Hz), 27.27, 22.35 I-42 N 226 ([M − H]⁺) 133-135(CDCl₃) δ 9.11 (bs, 1H), 7.44 (bs, 2H), 7.35-7.27 (m, 1H), 6.99 (s, 1H),4.03 (bs, 2H), 3.05 (hept, J = 6.9 Hz, 1H), 1.23 (d, J = 6.9 Hz, 6H)I-43 C 537 ([M − H]⁻) 219-222 (CDCl₃) δ 9.52 (s, 1H), 9.09 (s, 1H), 8.59(s, 1H), 8.26 (d, J = 8.2 Hz, 2H), 7.92 (s, 1H), 7.85-7.71 (m, 4H), 7.47(d, J = 7.5 Hz, 1H), 7.40 (d, J = 8.7 Hz, 2H), 7.21-7.08 (m, 2H),3.52-3.34 (m, 1H), 2.42 (s, 3H), 1.39 (d, J = 7.2 Hz, 6H) I-44 N — —(CDCl₃) δ 7.67 (d, J = 0.8 Hz, 1H), 7.34 (ddd, J = 7.8, 1.6, 0.5 Hz,1H), 7.20 (d, J = 7.8 Hz, 1H), 5.15 (pentet, J = 1.4 Hz, 1H), 4.93-4.89(m, 1H), 2.42 (s, 3H), 2.06 (dd, J = 1.4, 1.0 Hz, 3H); ¹³C NMR (101 MHz,CDCl3) δ 148.17, 142.71, 138.30, 136.16, 133.37, 130.33, 124.29, 115.18,23.32, 20.81 I-45 N — — (CDCl₃) δ 7.03 (d, J = 7.8 Hz, 1H), 6.65-6.56(m, 1H), 6.52 (d, J = 0.9 Hz, 1H), 3.58 (bs, 2H), 2.87 (hept, J = 6.8Hz, 1H), 1.24 (d, J = 6.8 Hz, 6H); ¹³C NMR (101 MHz, CDCl₃) δ 143.15,136.16, 129.82, 125.33, 119.79, 116.55, 27.37, 22.41, 20.96 I-46 N 224([M + H]⁺) 167-169 (CDCl₃) δ 8.95 (bs, 1H), 7.53-6.93 (m, 4H), 4.08 (bs,2H), 3.06 (heptet, J = 6.8 Hz, 1H), 2.33 (s, 3H), 1.19 (d, J = 6.8 Hz,6H) I-47 C 540 ([M + H]⁺) 194-196 (CDCl₃) δ 9.50 (s, 1H), 9.00 (s, 1H),8.60 (s, 1H), 8.26 (d, J = 8.4 Hz, 2H), 7.91 (s, 1H), 7.86-7.72 (m, 4H),7.49-7.36 (m, 3H), 7.27 (d, J = 9.2 Hz, 1H), 7.15 (d, J = 6.7 Hz, 1H),3.14 (heptet, J = 6.8 Hz, 1H), 2.37 (s, 3H), 1.29 (d, J = 6.9 Hz, 6H)I-48 N — — (CDCl₃) δ 7.96 (dd, J = 9.0, 5.1 Hz, 1H), 7.08 (ddd, J = 9.0,7.4, 2.8 Hz, 1H), 7.02 (dd, J = 8.7, 2.8 Hz, 1H), 5.20 (p, J = 1.5 Hz,1H), 4.96 (p, J = 1.0 Hz, 1H), 2.11-2.06 (m, 3H) I-49 N — — (CDCl₃) δ6.85 (dd, J = 10.3, 2.9 Hz, 1H), 6.72 (td, J = 8.3, 2.9 Hz, 1H), 6.60(dd, J = 8.6, 5.1 Hz, 1H), 3.49 (bs, 2H), 2.88 (hept, J = 6.8 1H), 1.24(d, J = 6.8 Hz, 6H); ¹³C NMR (101 MHz, CDCl₃) δ 156.92 (d, J_(CF) =235.0 Hz), 139.17 (d, J_(CF) = 2.1 Hz), 134.61 (d, J_(CF) = 6.2 Hz),116.55 (d, J_(CF) = 7.5 Hz), 112.69 (d, J_(CF) = 22.5 Hz), 112.17 (d,J_(CF) = 22.4 Hz), 27.90, 22.11 I-50 N 228 ([M + H]⁺) 163-167 (CDCl₃) δ8.88 (bs, 1H) 7.42 (bs, 1H), 7.03 (dd, J = 10.0, 2.9 Hz, 1H), 6.93 (ddd,J = 8.7, 7.7, 3.0 Hz, 1H), 4.03 (bs, 2H), 3.14-3.00 (m, 1H), 1.23 (d, J= 6.9 Hz, 6H) I-51 C 544 ([M + H]⁺) 219-221 (CDCl₃) δ 9.55 (s, 1H), 8.90(s, 1H), 8.59 (s, 1H), 8.30-8.21 (m, 2H), 7.92 (s, 1H), 7.85-7.74 (m,4H), 7.54 (dd, J = 8.8, 5.5 Hz, 1H), 7.40 (d, J = 8.6 Hz, 2H), 7.07 (dd,J = 10.0, 2.9 Hz, 1H), 6.97 (td, J = 8.2, 2.9 Hz, 1H), 3.24-3.08 (m,1H), 1.29 (d, J = 6.9 Hz, 6H) I-52 N — — (CDCl₃) δ 7.87-7.78 (m, 1H),7.19-7.09 (m, 1H), 5.20 (q, J = 1.5 Hz, 1H), 4.94 (q, J = 1.2 Hz, 1H),2.07 (t, J = 1.3 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 152.53 (dd, J_(CF)= 259.5, 12.5 Hz), 148.52 (dd, J_(CF) = 253.7, 13.8 Hz), 143.22, 141.38,137.23 (dd, J_(CF) = 7.1, 4.2 Hz), 119.27 (d, J_(CF) = 18.9 Hz), 116.39,114.49 (dd, J_(CF) = 21.9, 2.1 Hz), 23.12 I-53 N — — (CDCl₃) δ 6.97-6.84(m, 1H), 6.45 (dd, J = 12.1, 7.2 Hz, 1H), 3.57 (bs, 2H), 2.89-2.72 (m,1H), 1.22 (d, J = 6.8 Hz, 6H); ¹³C NMR (101 MHz, CDCl₃) δ 148.36 (dd,J_(CF) = 243.1, 13.4 Hz), 143.71 (dd, J_(CF) = 236.4, 12.4 Hz),139.79-139.13 (m), 128.70 (t, J_(CF) = 3.7 Hz), 114.07 (d, J_(CF) = 18.1Hz), 104.18 (d, J_(CF) = 19.8 Hz), 27.44, 22.20 I-54 N 246 ([M + H]⁺)169-170 (CDCl₃) δ 8.95 (s, 1H), 7.82-7.34 (m, 2H), 7.10 (dd, J = 11.7,8.5 Hz, 1H), 4.01 (s, 2H), 3.13-2.94 (m, 1H), 1.22 (d, J = 6.9 Hz, 6H)I-55 C 561 ([M + H]⁺) 217-221 (CDCl₃) δ 9.46 (s, 1H), 8.96 (s, 1H), 8.60(s, 1H), 8.31-8.22 (m, 2H), 7.92 (s, 1H), 7.84-7.75 (m, 4H), 7.60 (dd, J= 11.2, 7.7 Hz, 1H), 7.44-7.36 (m, 2H), 7.14 (dd, J = 11.7, 8.5 Hz, 1H),3.19-3.04 (m, 1H), 1.29 (d, J = 6.9 Hz, 6H) I-56 P* 402 ([M − H]⁻) —(CDCl₃) δ 8.64 (d, J = 1.1 Hz, 1H), 8.09 (m, 3H), 7.93 (m, 3H), 7.78 (d,J = 8.5 Hz, 3H), 7.30 (d, J = 7.9 Hz, 3H), 2.42 (s, 4H); ¹⁹F NMR (376MHz, CDCl3) δ −75.61, −75.63, −75.63, −182.14, −182.17, −182.18 I-57 P*418 ([M + H]⁺) — (CDCl₃) δ 10.09 (s, 1H), 8.71 (s, 1H), 8.39 (d, J = 8.3Hz, 2H), 8.01 (d, J = 8.3 Hz, 2H), 7.95 (m, 2H), 7.82 (d, J = 8.6 Hz,2H); ¹⁹F NMR (376 MHz, CDCl3) δ −75.57, −75.59, −182.14, −182.16,−182.18 I-58 N 210 ([M + H]⁺) — (CDCl₃) δ 8.97 (bs, 1H), 7.74-7.11 (m,5H), 4.06 (bs, 2H), 3.11 (hept, J = 6.9 Hz, 1H), 1.24 (d, J = 6.9 Hz,6H) I-59 C 609 ([M + H]⁺) — (CDCl₃) δ 9.59 (s, 1H), 9.05 (s, 1H), 8.69(s, 1H), 8.31-8.24 (m, 2H), 7.94 (d, J = 8.8 Hz, 3H), 7.85-7.74 (m, 4H),7.66 (dd, J = 7.7, 1.5 Hz, 1H), 7.39 (dd, J = 7.7, 1.8 Hz, 1H),7.37-7.27 (m, 2H), 3.19 (hept, J = 6.9 Hz, 1H), 1.32 (d, J = 6.8 Hz,6H); ¹⁹F NMR (376 MHz, CDCl₃) δ −75.58, −182.16 I-60- C 575 ([M + H]⁺)214-216 (DMSO-d₆) δ 11.87 (s, 1H), 10.08 (s, 1H), 9.44 (s, 1H), 8.20 (s,1H), 8.17-8.02 (m, 6H), 7.63 (d, J = 9.0 Hz, 2H), 7.39-7.35 (m, 1H),7.35-7.28 (m, 1H), 7.27-7.18 (m, 2H), 3.19-3.05 (m, 1H), 1.20 (d, J =6.9 Hz, 6H); ¹⁹F NMR (376 MHz, DMSO-d6) δ −85.20, −86.94 I-61 N 227([M + 2H]⁺) — (DMSO-d₆) δ 9.20 (brs, 1H), 8.89 (s, 1H), 7.20 (d, J =8.32 Hz, 1H), 6.71-6.77 (m, 2H), 4.71 (brs, 2H), 3.74 (s, 3H), 2.52-2.46(m, 2H), 1.11 (t, J = 7.56 Hz, 3H) I-62 C 591 ([M + H]⁺) — (DMSO-d₆) δ11.83 (s, 1H), 9.94 (s, 1H), 9.44 (s, 1H), 8.19 (s, 1H), 8.16-8.08 (m,4H), 8.05 (d, J = 8.3 Hz, 2H), 7.63 (d, J = 9.0 Hz, 2H), 7.14 (d, J =8.5 Hz, 1H), 6.85 (d, J = 2.9 Hz, 1H), 6.80 (dd, J = 8.5, 2.9 Hz, 1H),3.78 (s, 3H), 2.57 (q, J = 7.5 Hz, 2H), 1.16 (t, J = 7.6 Hz, 3H); ¹⁹FNMR (376 MHz, DMSO-d₆) δ −85.18, −86.92 NMR spectral data were acquiredusing a 400 MHz instrument unless otherwise noted. P*—Prepared accordingto methods described in Crouse et al. PCT Int. Appl. Publ. WO2009/102736A1 and Brown, et al, WO 2011017504 A1.

TABLE 3 Structures for Compounds ID Structure  1C

 2C

 3C

 4C

 5C

 6C

 7C

 8C

 9C

 10C

 11C

 12C

 13C

 14C

 15C

 16C

 17C

 18C

 19C

 20C

 21C

 22C

 23C

 24C

 25C

 26C

 27C

 28C

 29C

 30C

 31C

 32C

 33C

 34C

 35C

 36C

 37C

 38C

 39C

 40C

 41C

 42C

 43C

 44C

 45C

 46C

 47C

 48C

 49C

 50C

 51C

 52C

 53C

 54C

 55C

 56C

 57C

 58C

 59C

 60C

 61C

 62C

 63C

 64C

 65C

 66C

 67C

 68C

 69C

 70C

 71C

 72C

 73C

 74C

 75C

 76C

 77C

 78C

 79C

 80C

 81C

 82C

 83C

 84C

 85C

 86C

 87C

 88C

 89C

 90C

 91C

 92C

 93C

 94C

 95C

 96C

 97C

 98C

 99C

100C

101C

102C

103C

104C

105C

106C

107C

108C

109C

110C

111C

112C

113C

114C

115C

116C

117C

118C

119C

120C

121C

122C

123C

124C

125C

126C

127C

128C

129C

130C

131C

132C

133C

134C

135C

136C

137C

138C

139C

140C

141C

142C

143C

144C

145C

146C

147C

148C

149C

150C

151C

152C

153C

154C

155C

156C

157C

158C

159C

160C

161C

162C

163C

164C

165C

166C

167C

168C

169C

170C

171C

172C

173C

174C

175C

176C

177C

178C

179C

180C

181C

182C

183C

184C

185C

186C

187C

188C

189C

190C

191C

192C

193C

194C

195C

196C

197C

198C

199C

200C

201C

202C

203C

204C

205C

206C

207C

208C

209C

210C

211C

212C

213C

214C

215C

216C

217C

218C

219C

220C

221C

222C

223C

224C

225C

226C

227C

228C

229C

230C

231C

232C

233C

234C

235C

236C

237C

238C

239C

240C

241C

242C

243C

244C

245C

246C

247C

248C

249C

250C

251C

252C

253C

254C

255C

256C

257C

258C

259C

260C

261C

262C

263C

264C

TABLE 4 Analytical Data for Compounds in Table 3 Synthesis ¹H NMR, ¹³C,or ¹⁹F NMR ID Method MS mp (° C.) (δ)¹  1C D 540 (M+) — (DMSO-d₆) 8.61(s, 1H), 8.48 (s, 1H), 8.22 (d, J = 8.24 Hz, 2H), 8.17 (s, 1H), 7.89 (d,J = 8.24 Hz, 2H), 7.80 (d, J = 8.28 Hz, 2H), 7.41 (d, J = 8.28 Hz, 2H),7.19 (d, J = 8.24 Hz, 2H), 6.71 (d, J = 8.24 Hz, 2H), 2.99 (s, 6H), 2.42(s, 3H)  2C D 580 (M+) 168-171 (DMSO-d₆) 9.42 (s, 1H), 8.18-8.03 (m,5H), 7.78-7.69 (m, 2H), 7.61 (d, J = 8.26 Hz, 2H), 7.44 (d, J = 8.24 Hz,2H), 7.18 (m, 1H), 3.09-2.99 (m, 2H), 1.39-1.32 (m, 3H)  3C D 594180-182 (DMSO-d₆) 9.42 (s, 1H), 8.18-8.04 (m, 5H), 7.78-7.69 (m, 2H),7.61 (d, J = 8.26 Hz, 2H), 7.48 (d, J = 8.24 Hz, 2H), 7.19 (m, 1H),3.06-3.02 (m, 2H), 1.78-1.64 (m, 2H), 1.04-0.96 (m, 3H)  4C D 629 (M+)(DMSO-d₆) 8.57 (s, 1H), 8.48 (d, J = 5.5 Hz, 1H), 8.22 (d, J = 8.2 Hz,2H), 7.91-7.75 (m, 5H), 7.38 (d, J = 8.7 Hz, 2H), 7.22-7.07 (m, 3H),6.50-6.19 (m, 2H), 3.85 (d, J = 7.2 Hz, 1H), 3.75-3.64 (m, 1H), 2.33 (s,6H)  5C E 636 (M+) (300 MHz, CDCl₃) 8.56 (s, 1H), 8.54 (s, 1H), 8.23 (d,J = 8.3 Hz, 2H), 7.89 (d, J = 8.2 Hz, 3H), 7.79 (d, J = 9.0 Hz, 2H),7.38 (d, J = 8.7 Hz, 2H), 7.23-7.00 (m, 4H), 6.88-6.74 (m, 2H), 4.44 (s,2H), 2.33 (s, 6H)  6C D 645 (M + H) 196-198 (methanol-d₄) 9.16 (s, 1H),8.46 (s, 1H), 8.21 (d, J = 8.3 Hz, 2H), 8.03 (m, 6H), 7.52 (d, J = 8.3Hz, 4H), 7.28-6.91 (m, 3H), 4.39 (s, 2H), 2.08 (s, 6H)  7C E 636 (M+)(300 MHz, CDCl₃) 8.56 (m, 2H), 8.23 (d, J = 8.3 Hz, 2H), 7.88 (d, J =8.3 Hz, 3H), 7.79 (d, J = 9.0 Hz, 2H), 7.55-7.42 (m, 1H), 7.37 (d, J =9.0 Hz, 2H), 7.20-7.01 (m, 3H), 6.89-6.68 (m, 2H), 4.30 (s, 2H), 2.28(s, 6H)  8C E 684 (M+) (CDCl₃) 8.57 (s, 1H), 8.52 (s, 1H), 8.24 (d, J =8.3 Hz, 2H), 7.91-7.84 (m, 3H), 7.80 (d, J = 9.1 Hz, 2H), 7.39 (d, J =8.6 Hz, 4H), 7.18-7.03 (m, 5H), 4.32 (s, 2H), 2.29 (s, 6H)  9C E 620(M+) (CDCl₃) 8.57 (s, 1H), 8.47 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H), 7.87(d, J = 8.3 Hz, 2H), 7.80 (m, 3H), 7.39 (d, J = 8.4 Hz, 2H), 7.21-7.10(m, 3H), 3.93 (s, 2H), 2.35 (s, 6H), 0.13 (s, 9H)  10C D 600 (M+)(DMSO-d₆) 8.57 (s, 1H), 8.54 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H), 7.89 (d,J = 8.3 Hz, 2H), 7.87 (s, 1H), 7.80 (d, J = 9.0 Hz, 2H), 7.44-7.32 (m,4H), 7.31-7.19 (m, 3H), 7.19-7.00 (m, 3H), 4.34 (s, 2H), 2.31 (s, 6H) 11C D 618 (M+) (DMSO-d₆) 8.57 (s, 1H), 8.55 (s, 1H), 8.23 (d, J = 8.3Hz, 2H), 7.89 (d, J = 8.3 Hz, 2H), 7.86 (s, 1H), 7.83-7.73 (m, 2H), 7.48(td, J = 7.6, 1.7 Hz, 1H), 7.38 (d, J = 8.5 Hz, 2H), 7.23-6.91 (m, 6H),4.39 (s, 2H), 2.30 (s, 6H)  12C D 658 (M+) (DMSO-d₆) 8.57 (s, 1H), 8.51(s, 1H), 8.23 (d, J = 8.3 Hz, 2H), 7.94 (d, J = 8.3 Hz, 2H), 7.88 (d, J= 8.2 Hz, 2H), 7.86 (s, 1H), 7.79 (d, J = 9.0 Hz, 2H), 7.44 (d, J = 8.3Hz, 2H), 7.38 (d, J = 8.6 Hz, 2H), 7.20-7.05 (m, 3H), 4.35 (s, 2H), 3.88(s, 3H), 2.28 (s, 6H)  13C E 679 (M+) (DMSO-d₆) 8.59 (s, 1H), 8.51 (s,1H), 8.23 (d, J = 8.3 Hz, 2H), 7.93-7.76 (m, 7H), 7.53 (d, J = 8.2 Hz,2H), 7.39 (d, J = 8.7 Hz, 2H), 7.20-7.06 (m, 3H), 4.88 (s, 2H), 4.36 (s,2H), 2.28 (s, 6H)  14C E 658 (M+) (CDCl₃) 8.57 (s, 1H), 8.52 (s, 1H),8.23 (d, J = 8.3 Hz, 2H), 7.91-7.85 (m, 4H), 7.80 (d, J = 9.1 Hz, 2H),7.73 (d, J = 6.8 Hz, 1H), 7.52 (dd, J = 8.8, 6.9 Hz, 1H), 7.39 (d, J =9.0 Hz, 2H), 7.13-7.01 (m, 3H), 4.88 (s, 2H), 2.27 (s, 6H)  15C E 667(M+) (CDCl₃) 8.57 (s, 1H), 8.25-8.14 (m, 3H), 7.94-7.66 (m, 7H),7.52-7.35 (m, 6H), 7.16-7.03 (m, 3H), 4.54 (s, 2H), 2.32 (s, 6H)  16C E658 (M+) (CDCl₃) 8.57 (s, 1H), 8.49 (s, 1H), 8.24 (d, J = 8.4 Hz, 2H),7.88 (d, J = 8.3 Hz, 2H), 7.83-7.77 (m, 3H), 7.39 (d, J = 8.3 Hz, 2H),7.19-7.07 (m, 3H), 6.69-6.65 (m, 1H), 6.39-6.35 (m, 1H), 4.36 (s, 2H),2.29 (s, 6H)  17C E 678 (M+) (CDCl₃) 8.58 (s, 1H), 8.50 (s, 1H), 8.23(d, J = 8.3 Hz, 2H), 7.94-7.74 (m, 7H), 7.59 (d, J = 8.4 Hz, 2H), 7.38(d, J = 8.4 Hz, 2H), 7.20-7.04 (m, 3H), 4.37 (s, 2H), 3.01 (s, 3H), 2.29(s, 6H)  18C E 773 (M+) (CDCl₃) 8.59 (s, 1H), 8.46 (s, 1H), 8.22 (d, J =8.4 Hz, 2H), 7.86 (d, J = 8.4 Hz, 2H), 7.83-7.75 (m, 3H), 7.63 (d, J =8.4 Hz, 2H), 7.44 (d, J = 8.4 Hz, 2H), 7.38 (d, J = 8.4 Hz, 2H),7.17-7.05 (m, 3H), 7.03-6.98 (m, 3H), 6.89 (t, J = 8.6 Hz, 2H), 4.30 (s,2H), 2.24 (s, 6H)  19C E 728 (M+) (CDCl₃) 8.59 (s, 2H), 8.26 (d, J = 8.3Hz, 2H), 7.93 (d, J = 8.3 Hz, 2H), 7.89 (s, 1H), 7.82 (d, J = 9.1 Hz,2H), 7.40 (d, J = 8.3 Hz, 2H), 7.20-7.05 (m, 3H), 6.86 (s, 1H), 4.49 (s,2H), 3.98 (s, 3H), 2.31 (s, 6H)  20C E 681 (M+) (CDCl₃) 8.58 (s, 1H),8.38 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H), 7.86 (d, J = 8.3 Hz, 3H), 7.81(d, J = 9.1 Hz, 2H), 7.67-7.63 (m, 2H), 7.46-7.36 (m, 5H), 7.18-7.05 (m,3H), 4.24 (s, 2H), 2.47 (s, 3H), 2.29 (s, 6H)  21C E 596 (M+) (DMSO-d₆)8.58 (s, 1H), 8.15 (d, J = 8.4 Hz, 2H), 7.80 (d, J = 9.0 Hz, 2H),7.47-7.35 (m, 4H), 7.21-6.93 (m, 5H), 3.68 (t, J = 5.4 Hz, 2H), 3.35 (s,3H), 2.65 (t, J = 6.2 Hz, 2H), 2.29 (s, 6H)  22C E 626 (M+) (DMSO-d₆)8.59 (s, 1H), 8.52 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H), 7.95-7.75 (m, 5H),7.39 (d, J = 8.4 Hz, 2H), 7.21-7.06 (m, 3H), 5.80 (s, 2H), 4.12 (s, 2H),3.69-3.50 (m, 2H), 2.31 (s, 6H), 1.35-1.11 (m, 3H)  23C E 731 (M+)(DMSO-d₆) 8.58 (s, 1H), 8.50 (s, 1H), 8.22 (d, J = 8.2 Hz, 2H),7.93-7.70 (m, 5H), 7.45-7.28 (m, 8H), 7.23-7.03 (m, 3H), 5.79 (s, 2H),5.38-5.27 (m, 1H), 5.11 (s, 2H), 4.07-3.98 (m, 2H), 2.30 (s, 6H)  24C E626 (M+) (DMSO-d₆) 8.58 (s, 1H), 8.51 (s, 1H), 8.22 (d, J = 8.3 Hz, 2H),7.93-7.73 (m, 5H), 7.39 (d, J = 8.9 Hz, 2H), 7.21-7.07 (m, 3H), 5.76 (s,2H), 5.05-4.70 (m, 1H), 2.32 (s, 6H), 1.38-1.17 (m, 6H)  25C E 610 (M+)(DMSO-d₆) 8.59 (s, 1H), 8.52 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H),7.91-7.79 (m, 5H), 7.40 (d, J = 8.5 Hz, 2H), 7.18-7.06 (m, 3H), 5.73 (s,2H), 2.70-2.45 (m, 1H), 2.32 (s, 6H), 1.15 (s, 6H)  26C E 654 (M+)(DMSO-d₆) 8.58 (s, 1H), 8.21 (d, J = 8.4 Hz, 2H), 7.98 (d, J = 8.4 Hz,2H), 7.81 (d, J = 6.9 Hz, 2H), 7.69 (s, 1H), 7.40 (d, J = 8.8 Hz, 2H),6.63 (s, 2H), 5.73 (s, 2H), 3.80 (s, 3H), 2.64-2.53 (m, 1H), 2.58 (s,3H), 2.28 (s, 6H), 1.17 (d, J = 7.0 Hz, 6H)  27C E 640 (M+) (DMSO-d₆)8.58 (s, 1H), 8.50 (s, 1H), 8.23 (d, J = 8.2 Hz, 2H), 7.88 (d, J = 8.3Hz, 2H), 7.81 (d, J = 9.0 Hz, 2H), 7.74 (s, 1H), 7.39 (d, J = 8.6 Hz,2H), 6.63 (s, 2H), 5.71 (s, 2H), 3.79 (s, 3H), 2.74-2.43 (m, 1H), 2.27(s, 6H), 1.16 (d, J = 7.0 Hz, 6H)  28C E 761 (M+) (300 MHz, CDCl₃) 8.58(s, 1H), 8.48 (s, 1H), 8.22 (d, J = 8.3 Hz, 2H), 7.87 (d, J = 8.4 Hz,2H), 7.80 (d, J = 9.0 Hz, 2H), 7.74 (s, 1H), 7.45-7.28 (m, 7H), 6.63 (s,2H), 5.78 (s, 2H), 5.29 (m, 1H), 5.12 (s, 2H), 4.03 (d, J = 5.6 Hz, 2H),3.79 (s, 3H), 2.27 (s, 6H)  29C E 656 (M+) (300 MHz, CDCl₃) 8.58 (s,1H), 8.49 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H), 7.87 (d, J = 8.4 Hz, 2H),7.81 (d, J = 9.0 Hz, 2H), 7.72 (s, 1H), 7.40 (d, J = 8.7 Hz, 2H), 6.63(s, 2H), 5.78 (s, 2H), 4.11 (s, 2H), 3.80 (s, 3H), 3.59 (q, J = 7.0 Hz,2H), 2.27 (s, 6H), 1.24 (t, J = 7.1 Hz, 3H)  30C E 697 (M+) (300 MHz,CDCl₃) 8.60 (s, 1H), 8.50 (s, 1H), 8.22 (d, J = 8.3 Hz, 2H), 7.88 (d, J= 8.2 Hz, 2H), 7.82 (s, 1H), 7.80 (d, J = 9.0 Hz, 2H), 7.38 (d, J = 8.8Hz, 3H), 7.23-7.02 (m, 3H), 5.78 (s, 2H), 3.96 (s, 2H), 2.31 (s, 6H),1.44 (s, 9H)  31C E 582 (M+) (300 MHz, CDCl₃) 8.58 (s, 1H), 8.52 (s,1H), 8.23 (d, J = 8.3 Hz, 2H), 7.88 (m, 3H), 7.80 (d, J = 9.0 Hz, 2H),7.38 (d, J = 8.6 Hz, 2H), 7.14 (m, 3H), 5.72 (s, 2H), 2.32 (s, 6H), 2.09(s, 3H)  32C E 697 (M+) (CDCl₃) (Mixture of atropisomers) [8.61 (s),8.58 (s), 8.56 (s), 8.51 (s), 8.37 (d, J = 8.3 Hz), 8.23 (d, J = 8.4Hz), 8.21-8.14 (m), 8.00 (d, J = 8.4 Hz), 7.89 (d, J = 8.2 Hz),7.84-7.77 (m), 7.45-7.35 (m); 11H], 6.94 (s, 2H), [5.87 (s), 5.80 (s);2H], [4.12 (s), 4.11 (s); 2H], 3.83 (s, 3H), 3.69-3.44 (m, 2H),1.38-1.10 (m, 3H)  33C E 697 (M+) (CDCl₃) 8.57 (s, 1H), 8.51 (s, 1H),8.23 (d, J = 8.3 Hz, 2H), 7.88 (d, J = 8.4 Hz, 2H), 7.83-7.77 (m, 3H),7.39 (d, J = 8.4 Hz, 2H), 6.94 (s, 2H), 5.76 (s, 2H), 4.96-4.77 (m, 1H),3.82 (s, 3H), 1.30 (d, J = 6.3 Hz, 6H)  34C E 681 (M+) (CDCl₃) 8.57 (s,1H), 8.51 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H), 7.92-7.76 (m, 5H), 7.39 (d,J = 8.4 Hz, 2H), 6.93 (s, 2H), 5.73 (s, 2H), 3.82 (s, 3H), 2.59 (m, 1H),1.17 (d, J = 7.0 Hz, 6H)  35C E 636 (M+) (CDCl₃) 8.57 (s, 1H), 8.50 (s,1H), 8.23 (d, J = 8.4 Hz, 2H), 7.92-7.73 (m, 5H), 7.38 (d, J = 8.3 Hz,2H), 7.20-6.92 (m, 3H), 5.72 (s, 2H), 2.94-2.63 (m, 1H), 2.31 (s, 6H),2.02-1.38 (m, 8H)  36C E 624 (M+) (CDCl₃) 8.56 (s, 1H), 8.49 (s, 1H),8.23 (d, J = 8.3 Hz, 2H), 7.87 (d, J = 8.3 Hz, 2H), 7.84 (s, 1H), 7.79(d, J = 9.0 Hz, 2H), 7.38 (d, J = 8.4 Hz, 2H), 7.19-7.05 (m, 3H), 5.71(s, 2H), 2.31 (s, 6H), 1.20 (s, 9H)  37C E 691 (M + H) (CDCl₃) 8.59 (s,1H), 8.50 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H), 7.93-7.77 (m, 4H), 7.72 (s,1H), 7.40 (d, J = 9.0 Hz, 2H), 6.63 (s, 2H), 5.71 (s, 2H), 3.80 (s, 3H),2.68-2.48 (m, 1H), 2.28 (s, 6H), 1.16 (d, J = 7.0 Hz, 6H)  38C E 724(M+) (CDCl₃) 8.58 (s, 1H), 8.47 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H), 7.87(d, J = 8.3 Hz, 2H), 7.81 (d, J = 9.1 Hz, 2H), 7.71 (s, 1H), 7.39 (d, J= 9.0 Hz, 2H), 6.64 (s, 2H), 5.76 (dd, J = 37.3, 11.0 Hz, 2H), 4.19 (q,J = 6.9 Hz, 1H), 4.14-3.97 (m, 1H), 3.80 (s, 3H), 3.79-3.68 (m, 1H),2.27 (s, 6H), 1.47 (d, J = 6.9 Hz, 3H)  39C E 694 (M+) (CDCl₃) 8.58 (s,1H), 8.48 (s, 1H), 8.24 (d, J = 8.3 Hz, 2H), 7.87 (d, J = 8.3 Hz, 2H),7.83 (s, 1H), 7.81 (d, J = 9.1 Hz, 2H), 7.39 (d, J = 8.3 Hz, 2H),7.23-6.99 (m, 3H), 5.77 (dd, J = 36.4, 11.0 Hz, 2H), 4.19 (q, J = 6.9Hz, 1H), 4.14-3.97 (m, 1H), 3.84-3.65 (m, 1H), 2.31 (s, 6H), 1.47 (d, J= 6.9 Hz, 3H)  40C E 654 (M+) (CDCl₃) 8.57 (s, 1H), 8.48 (s, 1H), 8.23(d, J = 8.3 Hz, 2H), 7.87 (d, J = 8.3 Hz, 2H), 7.80 (d, J = 9.0 Hz, 2H),7.72 (s, 1H), 7.38 (d, J = 8.4 Hz, 2H), 6.62 (s, 2H), 5.70 (s, 2H), 3.79(s, 3H), 2.27 (s, 6H), 1.20 (s, 9H)  41C E 670 (M+) (CDCl₃) 8.58 (s,1H), 8.49 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H), 7.87 (d, J = 8.3 Hz, 2H),7.84 (s, 1H), 7.80 (d, J = 9.0 Hz, 2H), 7.38 (d, J = 8.4 Hz, 2H),7.23-6.96 (m, 3H), 5.77 (dd, J = 27.4, 10.9 Hz, 2H), 4.07 (q, J = 6.9Hz, 1H), 3.78-3.70 (m, 1H), 3.66-3.39 (m, 3H), 3.35 (s, 3H), 2.31 (s,6H), 1.42 (d, J = 6.9 Hz, 3H)  42C E 700 (M+) (CDCl₃) 8.58 (s, 1H), 8.48(s, 1H), 8.23 (d, J = 8.4 Hz, 2H), 7.87 (d, J = 8.3 Hz, 2H), 7.80 (d, J= 9.1 Hz, 2H), 7.71 (s, 1H), 7.39 (d, J = 8.3 Hz, 2H), 6.63 (s, 2H),5.76 (dd, J = 27.8, 10.9 Hz, 2H), 4.07 (q, J = 6.9 Hz, 1H), 3.79 (s,3H), 3.79-3.70 (m, 1H), 3.63-3.45 (m, 3H), 3.35 (s, 3H), 2.27 (s, 6H),1.42 (d, J = 6.9 Hz, 3H)  43C E 666 (M+) (CDCl₃) 8.57 (s, 1H), 8.49 (s,1H), 8.22 (d, J = 8.3 Hz, 2H), 7.87 (d, J = 8.3 Hz, 2H), 7.79 (d, J =9.1 Hz, 2H), 7.74 (s, 1H), 7.38 (d, J = 8.3 Hz, 2H), 6.62 (s, 2H), 5.71(s, 2H), 3.79 (s, 3H), 2.85-2.65 (m, 1H), 2.27 (s, 6H), 1.98-1.51 (m,8H)  44C E 668 (M+) (CDCl₃) 8.59 (s, 1H), 8.55 (s, 1H), 8.22 (d, J = 8.3Hz, 2H), 7.87 (d, J = 8.3 Hz, 2H), 7.84-7.74 (m, 3H), 7.38 (d, J = 8.4Hz, 2H), 6.63 (s, 2H), 5.85-5.73 (m, 2H), 4.54-4.47 (m, 1H), 4.03 (dd, J= 14.7, 6.9 Hz, 1H), 3.91 (dd, J = 13.8, 7.4 Hz, 1H), 3.79 (s, 3H), 2.27(s, 6H), 2.09-1.83 (m, 4H)  45C E 746 (M + H) 132-137 (CDCl₃) 8.68 (s,1H), 8.49 (s, 1H), 8.24 (d, J = 8.3 Hz, 2H), 7.93 (d, J = 8.4 Hz, 2H),7.88 (d, J = 8.3 Hz, 2H), 7.81 (d, J = 8.5 Hz, 2H), 7.73 (s, 1H), 7.35(s, 5H), 6.64 (s, 2H), 5.78 (s, 2H), 5.24 (s, 1H), 5.12 (s, 2H), 4.04(d, J = 5.5 Hz, 2H), 3.80 (s, 3H), 2.28 (s, 6H)  46C E 624 108-113(CDCl₃) 8.68 (s, 1H), 8.50 (s, 1H), 8.24 (d, J = 8.3 Hz, 2H), 7.98-7.69(m, 7H), 6.63 (s, 2H), 5.71 (s, 2H), 3.80 (s, 3H), 2.59 (heptet, J = 7.0Hz, 1H), 2.29 (d, J = 6.9 Hz, 6H), 1.16 (d, J = 7.0 Hz, 6H)  47C E149-151 (acetone-d₆) 9.20 (s, 1H), 8.52 (s, 1H), 8.40-8.21 (m, 2H),8.21-8.01 (m, 4H), 7.61 (d, J = 8.3 Hz, 2H), 7.32-6.94 (m, 3H), 3.83 (s,2H), 2.34 (s, 6H)  48C E 599 (M + H) 128-137 (acetone-d₆) 9.18 (s, 1H),8.83 (s, 1H), 8.67-7.82 (m, 8H), 7.60 (d, J = 8.4 Hz, 2H), 6.78 (s, 2H),3.99-3.72 (m, 3H), 2.41-2.20 (m, 6H)  49C E 619 (M + H) 177-185(methanol-d₄) 9.23 (s, 1H), 8.62 (s, 1H), 8.29 (m, 2H), 8.17-7.98 (m,4H), 7.60-7.45 (m, 2H), 7.41-7.19 (m, 3H), 4.22 (s, 2H), 2.34 (s, 6H) 50C E 635 (M + H) 193-196 (methanol-d₄) 9.23 (s, 1H), 8.57 (s, 1H),8.28 (m, 3H), 8.09-7.98 (m, 4H), 7.50 (m, 4H), 4.19-4.11 (m, 2H), 3.85(s, 3H), 2.36 (s, 3H)  51C E 649 (M + H) 176-179 (methanol-d₄) 9.23 (s,1H), 8.60 (s, 1H), 8.30 (m, 2H), 8.14-8.00 (m, 4H), 7.52 (m, 2H), 6.81(s, 2H), 4.22 (s, 2H), 3.84-3.81 (m, 3H), 2.33 (s, 6H)  52C E 599 (M +H) 168-178 (methanol-d₄) 9.21 (s, 1H), 8.44 (s, 1H), 8.27 (d, J = 8.1Hz, 2H), 8.09-7.98 (m, 4H), 7.52 (d, J = 8.3 Hz, 2H), 7.40 (d, J = 8.7Hz, 2H), 6.97 (d, J = 8.8 Hz, 2H), 5.40 (s, 1H), 4.37-4.13 (m, 2H), 3.79(s, 3H), 1.79 (m, 3H)  53C E 617 (M + H) 168-170 (methanol-d₄) 9.21 (s,1H), 8.44 (m, 1H), 8.28 (d, J = 8.2 Hz, 2H), 8.11-7.99 (m, 4H), 7.52 (d,J = 8.4 Hz, 2H), 7.25 (m, 2H), 7.14 (t, J = 8.5 Hz, 1H), 5.42 (m, 1H),4.25 (m, 2H), 3.88 (s, 3H), 1.75 (m, 3H)  54C E 569 (M + H) 167-170(methanol-d₄) 9.23 (s, 1H), 8.46 (s, 1H), 8.27 (m, 2H), 8.05 (m, 4H),7.57-7.39 (m, 7H), 5.41 (m, 1H), 4.24 (m, 2H), 1.79 (m, 3H)  55C E 624(M + H)  90-97 (methanol-d₄) 9.12 (s, 1H), 8.46 (s, 1H), 8.14 (m, 2H),7.99 (m, 3H), 7.78 (s, 1H), 7.49 (d, J = 8.5 Hz, 2H), 7.12 (m, 3H), 3.69(s, 2H), 3.22-2.80 (m, 2H), 2.25 (s, 6H), 2.03 (s, 2H), 1.93-1.66 (m,1H), 0.92 (m, J = 9.7 Hz, 6H)  56C E 765 (M + H) 148-151 (methanol-d₄)9.18 (s, 1H), 8.59 (s, 1H), 8.30 (d, J = 8.1 Hz, 2H), 8.12 (m, 2H),8.07-8.00 (m, 2H), 7.58-7.43 (m, 2H), 7.33 (dd, J = 8.6, 6.5 Hz, 1H),7.25 (d, J = 7.6 Hz, 2H), 4.02 (m, 2H), 3.97-3.75 (m, 2H), 3.21 (d, J =6.9 Hz, 2H), 2.90 (m, 1H), 2.59 (m, 1H), 2.35 (s, 6H), 1.84 (m, 2H),1.78-1.63 (m, 2H), 1.44 (s, 9H), 1.29 (m, 3H)  57C E 737 (M + H) 151-153(methanol-d₄) 9.20 (s, 1H), 8.65 (s, 1H), 8.30 (m, 2H), 8.21-7.96 (m,4H), 7.53 (d, J = 8.4 Hz, 2H), 7.35 (dd, J = 8.5, 6.5 Hz, 1H), 7.28 (d,J = 7.5 Hz, 2H), 4.44 (s, 2H), 3.91-3.40 (m, 9H), 2.38 (s, 6H), 1.50 (s,9H)  58C E 725 (M + H) 125-127 (methanol-d₄) 9.18 (s, 1H), 8.61 (s, 1H),8.31 (m, 2H), 8.14 (m, 2H), 8.06 (d, J = 9.0 Hz, 2H), 7.53 (d, J = 8.5Hz, 2H), 7.32 (dt, J = 26.0, 7.0 Hz, 3H), 4.02 (s, 2H), 3.38-3.34 (m,2H), 3.22-3.03 (m, 2H), 2.37 (s, 6H), 1.74 (m, 2H), 1.45 (s, 9H)  59C E755 (M + H) 147-149 (methanol-d₄) 9.18 (s, 1H), 8.62 (s, 1H), 8.38-7.97(m, 6H), 7.51 (d, J = 8.4 Hz, 2H), 7.32 (dd, J = 8.5, 6.6 Hz, 1H), 7.25(d, J = 7.6 Hz, 2H), 4.40 (s, 1H), 4.06 (m, 2H), 3.91-3.74 (m, 2H),3.56-3.41 (m, 1H), 2.36 (s, 6H), 1.44 (s, 9H)  60C E 755 (M + H) 136-139(methanol-d₄) 9.16 (s, 1H), 8.58 (s, 1H), 8.28 (d, J = 7.4 Hz, 2H),8.16-7.76 (m, 4H), 7.52 (p, J = 8.8 Hz, 2H), 6.83 (m, 2H), 4.04 (d, J =8.5 Hz, 2H), 3.90-3.73 (m, 3H), 3.55-3.37 (m, 2H), 3.14-2.75 (m, 3H),2.30 (s, 6H), 1.99-1.80 (m, 2H), 1.43-1.31 (m, 2H)  61C E 738 (M + H)70-79 (methanol-d₄) 9.12 (s, 1H), 8.12-8.07 (m, dec 2H), 8.02-7.96 (m,2H), 7.55-7.50 (m, 2H), 7.50-7.45 (m, 2H), 7.43 (d, J = 7.7 Hz, 1H),7.31 (d, J = 7.6 Hz, 2H), 4.03 (s, 2H), 3.25 (dt, J = 15.5, 7.0 Hz, 4H),2.84 (s, 3H), 2.04 (s, 6H), 1.81-1.66 (m, 2H), 1.44 (s, 9H)  62C K 665(M + H) 110-120 (methanol-d₄) δ 9.18 (s, 1H), 8.56 (m, 1H), 8.26 (m,2H), 8.16-7.84 (m, 4H), 7.52 (m, 2H), 7.27 (m, 1H), 7.22 (m, 2H), 4.00(s, 2H), 3.28 (m, 3H), 3.06-2.83 (m, 1H), 2.75 (t, J = 12.2 Hz, 1H),2.34 (s, 6H), 2.21-1.83 (m, 4H), 1.72 (m, 1H), 1.47-1.19 (m, 2H)  63C K655 (M + H)  98-110 (methanol-d₄) 9.18 (s, 1H), 8.63 (s, 1H), 8.28 (m,2H), 8.13-7.97 (m, 4H), 7.51 (d, J = 8.3 Hz, 2H), 7.31 (dd, J = 8.5, 6.5Hz, 1H), 7.24 (d, J = 7.6 Hz, 2H), 4.32-4.07 (m, 3H), 3.98-3.81 (m, 1H),3.72 (s, 1H), 2.35 (s, 6H)  64C K 655 (M + H)  83-112 (methanol-d₄) 9.19(s, 1H), 8.58 (s, 1H), 8.28 (m, 2H), 8.14-7.97 (m, 4H), 7.51 (m, 2H),6.78 (s, 2H), 4.00 (m, 2H), 3.81 (s, 3H), 3.10-2.93 (m, 4H), 2.30 (s,6H), 1.91 (m, 2H)  65C K 667 (M + H) 128 dec (methanol-d₄) 9.20 (s, 1H),8.65 (s, 1H), 8.27 (m 2H), 8.11-7.99 (m, 4H), 7.52 (d, J = 8.3 Hz, 2H),6.78 (s, 2H), 4.40 (s, 2H), 3.87 (m, 4H), 3.53 (s, 3H), 2.32 (s, 6H),1.33 (m, 4H)  66C K 625 (M + H) 100-105 (methanol-d₄) 9.20 (s, 1H), 8.56(s, 1H), 8.27 (m, 2H), 8.12-7.99 (m, 3H), 7.53 (d, J = 8.4 Hz, 2H), 7.24(m, 4H), 3.99 (s, 2H), 3.42 (m, 2H), 3.05 (m, 2H), 2.36 (s, 6H),1.99-1.88 (m, 2H)  67C K 636 (M + H) 237-240 (methanol-d₄) 9.20 (s, 1H),8.74 (s, 1H), dec 8.33-8.25 (m, 2H), 8.12-7.98 (m, 4H), 7.53 (d, J = 8.3Hz, 2H), 7.33 (dd, J = 8.5, 6.4 Hz, 1H), 7.26 (d, J = 7.5 Hz, 2H), 4.55(s, 2H), 3.92 (m, 4H), 3.37 (m, 2H), 3.31 (m, 2H), 2.38 (s, 6H)  69C F581 (M + H) 188-190 (CDCl₃) 8.56 (s, 1H), 8.33 (s, 1H), 8.22 (d, J = 8.1Hz, 2H), 7.90-7.70 (m, 4H), 7.39 (d, J = 8.7 Hz, 2H), 6.72 (s, 2H), 4.01(s, 2H), 3.87-3.73 (s, 3H), 2.18 (s, 6H)  70C F 592 (M+) 134-138 (CDCl₃)8.65 (s, 1H), 8.31 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H), 7.83 (m, 4H), 7.50(d, J = 8.1 Hz, 2H), 7.45-7.38 (m, 3H), 4.05 (s, 2H)  71C F 551 (M + H)104-111 (CDCl₃) 8.62 (s, 1H), 8.32 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H),7.88-7.74 (m, 4H), 7.40 (d, J = 8.3 Hz, 2H), 7.34-7.26 (m, 1H), 7.20 (d,J = 7.5 Hz, 2H), 4.02 (s, 2H), 2.22 (s, 6H)  72C F 565 (M + H) 118-121(CDCl₃) 8.58 (s, 1H), 8.33 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H), 7.81 (m,4H), 7.40 (d, J = 8.3 Hz, 2H), 7.01 (d, J = 0.4 Hz, 2H), 4.01 (s, 2H),2.34 (s, 3H), 2.17 (s, 6H)  73C F 565 (M + H) 145-150 (CDCl₃) 8.58 (s,1H), 8.30 (s, 1H), 8.23 (d, J = 8.3 Hz, 1H), 7.81 (m, 2H), 7.49 (d, J =4.0 Hz, 1H), 7.40 (d, J = 8.4 Hz, 1H), 7.34 (s, 1H), 7.18 (d, J = 7.8Hz, 1H), 4.01 (d, J = 1.4 Hz, 1H), 2.83 (heptet, J = 6.8 Hz, 1H), 1.23(t, J = 6.6 Hz, 3H).  74C G 682 (M + H) 190-193 (methanol-d₄) 9.20 (s,1H), 8.38 (s, 1H), 8.31-8.24 (m, 2H), 8.08-8.00 (m, 2H), 7.95-7.88 (m,2H), 7.55-7.48 (m, 3H), 7.48-7.36 (m, 5H), 7.31 (d, J = 7.7 Hz, 2H),3.60 (q, J = 7.2 Hz, 4H), 2.20 (s, 6H), 1.07 (t, J = 7.2 Hz, 6H);  75C G617 (M+) (CDCl₃) 8.56 (s, 1H), 8.23 (s, 1H), 8.19 (d, J = 8.4 Hz, 2H),7.84-7.73 (m, 5H), 7.41-7.33 (m, 3H), 7.21 (d, J = 7.2 Hz, 2H), 7.16 (s,1H), 7.12 (d, J = 3.2 Hz, 1H), 2.20 (s, 6H).  76C G 711 (M+) (CDCl₃)8.56 (s, 1H), 8.25 (s, 1H), 8.20 (d, J = 8.4 Hz, 2H), 7.80 (dd, J = 8.7,5.6 Hz, 4H), 7.48-7.34 (m, 8H), 7.26 (d, J = 7.7 Hz, 2H), 7.08 (s, 1H),2.20 (s, 6H)  77C G 655 (M + H) 261-263 (methanol-d₄) 9.14 (s, 1H),8.21-8.13 (m, 3H), 8.06-7.99 (m, 2H), 7.86-7.75 (m, 4H), 7.50 (d, J =8.3 Hz, 2H), 7.28-7.18 (m, 3H), 7.14 (d, J = 7.9 Hz, 2H), 6.72 (s, 1H),0.09-−0.09 (m, 6H)  78C G 694 (M + H) (CDCl₃) 8.55 (s, 1H), 8.22 (s,1H), 8.18 (d, J = 8.3 Hz, 2H), 7.79 (dd, J = 8.7, 5.1 Hz, 4H), 7.37 (d,J = 9.0 Hz, 2H), 7.23-6.94 (m, 7H), 6.26 (s, 1H), 2.17 (s, 6H)  79C G678 (M + H) (CDCl₃) 8.55 (s, 1H), 8.23 (s, 1H), 8.19 (d, J = 8.3 Hz,2H), 7.79 (d, J = 8.7 Hz, 4H), 7.43 (d, J = 8.3 Hz, 2H), 7.37 (d, J =8.9 Hz, 2H), 7.23-7.16 (m, 3H), 7.08 (d, J = 7.4 Hz, 2H), 6.35 (s, 1H),2.18 (s, 6H)  80C G 609 (M + H) 215-219 (methanol-d₄) 9.23 (s, 1H), 8.40(s, 1H), 8.26 (m, 2H), 8.22 (s, 1H), 8.07-8.00 (m, 3H), 7.91 (d, J = 8.4Hz, 2H), 7.51 (d, J = 8.3 Hz, 2H), 6.90 (s, 1H), 3.88 (s, 3H), 2.13 (s,6H)  81C I 551 (M + H) 209-213 (CDCl₃) 9.42 (s, 1H), 8.59 (s, 1H), 8.28(d, J = 8.4 Hz, 2H), 8.01 (d, J = 8.3 Hz, 2H), 7.80-7.77 (m, 2H),7.43-7.34 (m, 2H), 7.07 (d, J = 7.5 Hz, 2H), 6.98 (dd, J = 8.2, 6.7 Hz,1H), 3.90 (s, 2H), 2.17 (s, 6H)  82C I 565 (M + H) 225-232 (CDCl₃) 9.46(s, 1H), 8.60 (s, 1H), 8.29 (d, J = 8.4 Hz, 2H), 8.02 (d, J = 8.4 Hz,2H), 7.89-7.76 (m, 2H), 7.40 (d, J = 8.3 Hz, 2H), 6.88 (s, 2H), 3.90 (s,2H), 2.28 (s, 3H), 2.13 (s, 6H).  83C I 581 (M + H) 211-215 (CDCl₃) 9.44(s, 1H), 8.60 (s, 1H), 8.30 (d, J = 8.4 Hz, 2H), 8.02 (d, J = 8.4 Hz,2H), 7.82 (d, J = 9.1 Hz, 2H), 7.40 (d, J = 8.3 Hz, 2H), 6.63 (s, 2H),3.90 (s, 2H), 3.78 (s, 3H), 2.15 (s, 6H)  84C I 591 250 dec (CDCl₃) 9.42(s, 1H), 8.40 (s, 1H), 8.18 (d, J = 8.24 Hz, 2H), 8.07 (d, J = 8.28 Hz,2H), 7.89 (d, J = 8.24 Hz, 2H), 7.76 (d, J = 8.28 Hz, 2H), 7.64-7.58 (m,3H), 4.42 (s, 2H)  85C I 551 (M + H) 146-149 (CDCl₃) δ 9.36 (s, 1H),8.60 (s, 1H), 8.30 (d, J = 8.4 Hz, 2H), 8.01 (d, J = 8.4 Hz, 2H),7.86-7.77 (m, 2H), 7.40 (d, J = 8.3 Hz, 2H), 7.32 (dd, J = 6.9, 2.3 Hz,1H), 7.24-7.12 (m, 2H), 6.91 (dd, J = 7.1, 2.0 Hz, 1H), 3.93 (s, 2H),3.15-2.97 (m, 1H), 1.21 (d, J = 6.9 Hz, 6H)  86C J 566 (M + H) 163-169(CDCl₃) δ 8.81 (bs, 1H), 8.57 (s, 1H), 8.20 (d, J = 8.3 Hz, 2H),7.87-7.75 (m, 4H), 7.39 (d, J = 8.3 Hz, 2H), 7.32-7.25 (m, 1H), 7.10(2dt, J = 7.4, 1.5 Hz, 2H), 6.83 (d, J = 6.5 Hz, 1H), 3.96 (t, J = 6.1Hz, 2H), 3.13 (heptet, J = 6.9 Hz, 1H), 2.99-2.88 (m, 2H), 2.49-2.36 (m,2H), 1.29-1.21 (m, 6H).  87C J 550 (M + H) 187-189 (CDCl₃) δ 8.81 (s,1H), 8.66 (s, 1H), 8.21 (d, J = 8.3 Hz, 2H), 7.92 (d, J = 8.4 Hz, 2H),7.81 (t, J = 10.2 Hz, 4H), 7.30-7.26 (m, 2H), 7.17-7.04 (m, 1H), 6.83(d, J = 6.4 Hz, 1H), 3.96 (t, J = 6.1 Hz, 2H), 3.13 (heptet, J = 6.9 Hz,1H), 2.97-2.90 (m, 2H), 2.47-2.38 (m, 2H), 1.25 (d, J = 7.5 Hz, 6H). 88C F 579.2 (M + H) 178-182 (CDCl₃) δ 8.58 (s, 1H), 8.30 (s, 1H), 8.22(d, J = 8.3 Hz, 2H), 7.82 (dd, J = 8.7, 7.2 Hz, 4H), 7.48 (dd, J = 4.1,1.3 Hz, 2H), 7.40 (d, J = 8.3 Hz, 2H), 7.37-7.30 (m, 1H), 7.17 (m, 1H),4.23 (dq, J = 14.5, 7.2 Hz, 1H), 2.83 (dd, J = 14.6, 6.9 Hz, 1H), 1.79(d, J = 7.2 Hz, 3H), 1.22 (ddd, J = 12.1, 6.9, 1.9 Hz, 6H).  89C F 559(M + H) 205-206 (CDCl₃) δ 8.58 (s, 1H), 8.32 (s, 1H), 8.23 (d, J = 8.4Hz, 2H), 7.90-7.75 (m, 4H), 7.52-7.44 (m, 1H), 7.40 (d, J = 8.3 Hz, 2H),7.10 (dd, J = 8.6, 7.4 Hz, 2H), 4.04 (s, 2H).  90C F 566 (M + H) 148-151(CDCl₃) δ 8.58 (s, 1H), 8.31 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H), 7.82 (t,J = 8.5 Hz, 4H), 7.46-7.31 (m, 3H), 7.25-7.18 (m, 2H), 4.02 (s, 2H),2.53 (q, J = 7.6 Hz, 2H), 2.21 (s, 3H), 1.26-1.16 (m, 3H).  91C F 554(M + H) 227-235 (CDCl₃) δ 8.58 (s, 1H), 8.36 (s, 1H), 8.23 (d, J = 8.3Hz, 2H), 7.88-7.76 (m, 4H), 7.49-7.35 (m, 3H), 7.01 (dd, J = 8.5, 2.5Hz, 1H), 6.96 (dd, J = 7.8, 1.0 Hz, 1H), 6.91 (t, J = 2.2 Hz, 1H), 3.98(s, 2H), 3.85 (s, 3H).  92C F 554 (M + H) 104-108 (CDCl₃) δ 8.58 (s,1H), 8.32 (s, 1H), 8.22 (d, J = 8.4 Hz, 2H), 7.86-7.77 (m, 4H),7.50-7.43 (m, 1H), 7.40 (d, J = 8.3 Hz, 2H), 7.32-7.27 (m, 1H),7.14-7.04 (m, 2H), 4.01 (d, J = 17.2 Hz, 1H), 3.94 (d, J = 17.3 Hz, 1H),3.84 (s, 3H).  93C F 572 (M + H) 183-186 (CDCl₃) δ 8.58 (s, 1H), 8.31(s, 1H), 8.27-8.18 (m, 2H), 7.88-7.77 (m, 4H), 7.43-7.37 (m, 3H), 7.34(t, J = 7.8 Hz, 1H), 7.30-7.26 (m, 1H), 4.07 (d, J = 17.4 Hz, 1H), 4.00(d, J = 17.4 Hz, 1H), 2.29 (s, 3H).  94C F 552 (M + H) 134-136 (CDCl₃) δ8.58 (s, 1H), 8.31 (s, 1H), 8.23 (d, J = 8.4 Hz, 2H), 7.86-7.78 (m, 4H),7.49-7.32 (m, 5H), 7.24-7.18 (m, 1H), 4.06-3.94 (m, 2H), 2.56 (q, J =7.6 Hz, 2H), 1.26-1.18 (m, 3H).  95C F 576.1 (M + H) 195-201 (CDCl₃) δ8.59 (d, J = 4.8 Hz, 1H), 8.26 (m, 3H), 7.89-7.74 (m, 4H), 7.52-7.31 (m,4H), 7.24-7.13 (m, 1H), 4.05 (d, J = 0.9 Hz, 2H).  96C F 600 (M + H)182-185 (300 MHz, CDCl₃) δ 8.58 (s, 1H), 8.33 (d, J = 7.9 Hz, 1H), 8.24(s, 1H), 8.21 (s, 1H), 7.86-7.76 (m, 4H), 7.53 (t, J = 5.9 Hz, 3H),7.44-7.29 (m, 8H), 3.80-3.73 (m, 1H), 3.59-3.51 (m, 1H).  97C F 567 (M +H) 234-236 (CDCl₃) δ 8.57 (s, 1H), 8.37 (s, 1H), 8.23 (d, J = 8.4 Hz,2H), 7.89-7.73 (m, 4H), 7.45-7.29 (m, 3H), 6.79 (dd, J = 8.2, 2.2 Hz,1H), 6.70 (d, 1H), 6.57 (s, 1H), 3.96 (s, 2H), 2.98 (s, 6H)  98C F 612(M + H) 225-226 (CDCl₃) δ 8.55 (s, 1H), 8.29 (s, 1H), 8.21 (d, J = 8.4Hz, 2H), 7.86-7.71 (m, 4H), 7.42-7.23 (m, 3H), 6.63 (d, J = 8.5 Hz, 2H),4.07 (q, J = 7.0 Hz, 4H), 3.94 (s, 2H), 1.31 (t, J = 7.0 Hz, 6H)  99C F679 (M − H) 230-231 (CDCl₃) δ 8.58 (s, 1H), 8.32 (s, 1H), 8.23 (d, J =8.4 Hz, 2H), 7.89-7.77 (m, 4H), 7.70 (d, J = 8.1 Hz, 2H), 7.40 (d, J =8.3 Hz, 2H), 7.29-7.20 (m, 1H), 4.04 (s, 2H) 100C F 602 (M + H) 118-120(CDCl₃) δ 8.58 (s, 1H), 8.30 (s, 1H), 8.22 (d, J = 8.4 Hz, 2H),7.93-7.70 (m, 4H), 7.39 (d, J = 9.0 Hz, 2H), 7.28 (t, 1H), 7.19 (d, J =7.7 Hz, 2H), 4.01 (s, 2H), 2.21 (s, 6H). 101C F 583 (M + H) 106-107(CDCl₃) δ 8.60 (s, 1H), 8.32 (s, 1H), 8.23 (d, J = 8.4 Hz, 2H),7.89-7.74 (m, 4H), 7.39 (d, J = 8.3 Hz, 2H), 6.56 (s, 1H), 4.01 (s, 2H),3.94 (s, 3H), 2.32 (s, 3H), 2.16 (s, 3H) 102C F 589 (M − H) 123-126(CDCl₃) δ 8.27 (s, 1H), 7.95-7.71 (m, 5H), 7.60 (d, J = 1.3 Hz, 1H),7.53-7.43 (m, 4H), 7.45-7.32 (m, 3H), 4.04 (s, 2H) 103C F 551 (M + H)194-196 (CDCl₃) δ 8.28 (s, 1H), 7.93 (dd, J = 5.4, 4.1 Hz, 3H), 7.78 (m,4H), 7.36-7.23 (m, 3H), 7.19 (d, J = 7.6 Hz, 2H), 6.81 (d, J = 2.5 Hz,1H), 4.00 (s, 2H), 2.21 (s, 6H) 104C F 551 (M + H) 100-102 (CDCl₃) δ8.27 (s, 1H), 8.16 (s, 1H), 8.03 (s, 1H), 7.80-7.71 (m, 4H), 7.57 (d, J= 8.3 Hz, 2H), 7.30 (dd, J = 28.7, 5.8 Hz, 3H), 7.19 (d, J = 7.6 Hz,2H), 4.01 (s, 2H), 2.21 (s, 6H) 105C F 586 (M + H) 209-211 (CDCl₃) δ8.58 (s, 1H), 8.31 (s, 1H), 8.23 (d, J = 7.8 Hz, 2H), 7.82 (m, 4H), 7.39(d, J = 8.0 Hz, 2H), 7.19 (s, 2H), 4.01 (s, 2H), 2.19 (s, 6H) 106C F 558(M + H) 180-182 (CDCl₃) δ 8.58 (s, 1H), 8.30 (s, 1H), 8.22 (d, J = 8.2Hz, 2H), 7.81 (m, 4H), 7.58 (dd, J = 6.0, 3.3 Hz, 1H), 7.43 (ddd, J =23.4, 11.3, 5.5 Hz, 5H), 4.02 (dd, J = 29.9, 17.4 Hz, 2H) 107C F 596(M + H) 227-232 (CDCl₃) δ 8.58 (s, 1H), 8.32 (s, 1H), 8.22 (dd, J =10.0, 8.6 Hz, 4H), 7.82 (m, 4H), 7.49 (d, J = 8.5 Hz, 2H), 7.40 (d, J =8.6 Hz, 2H), 4.42 (q, J = 7.1 Hz, 2H), 4.00 (s, 2H), 1.41 (t, J = 7.1Hz, 3H) 108C F 580 (M + H) 167-171 (CDCl₃) δ 8.58 (s, 1H), 8.28 (d, J =15.0 Hz, 1H), 8.23 (d, J = 8.3 Hz, 2H), 7.87-7.76 (m, 4H), 7.53-7.30 (m,5H), 7.18 (ddd, J = 7.8, 4.2, 1.2 Hz, 1H), 4.03-3.98 (m, 2H), 2.53 (dd,J = 14.1, 7.0 Hz, 1H), 1.77-1.56 (m, 2H), 1.26-1.16 (m, 3H), 0.78 (td, J= 7.4, 2.3 Hz, 3H). 109C F 652 (M + H) 105-111 (CDCl₃) δ 8.25 (s, 1H),7.73 (d, J = 7.4 Hz, 4H), 7.55-7.43 (m, 2H), 7.43-7.36 (m, 1H), 7.10 (t,J = 11.6 Hz, 4H), 4.90-4.79 (m, 1H), 4.04 (s, 2H), 3.76 (s, 3H),3.73-3.62 (m, 1H), 3.52-3.35 (m, 1H) 110C F 611 (M + H) Oil (CDCl₃) δ8.25 (s, 1H), 7.82-7.64 (m, 4H), 7.30 (t, 1H), 7.22-6.99 (m, 6H), 4.83(dd, J = 12.8, 6.5 Hz, 1H), 4.00 (s, 2H), 3.89-3.59 (m, 4H), 3.44 (dd, J= 17.2, 6.5 Hz, 1H), 2.20 (s, 6H). 111C F 580 (M + H) 209-210 (CDCl₃) δ8.58 (s, 1H), 8.30 (s, 1H), 8.23 (d, J = 8.4 Hz, 2H), 7.86-7.77 (m, 4H),7.39 (t, J = 7.8 Hz, 3H), 7.34-7.27 (m, 1H), 7.20 (d, J = 7.4 Hz, 1H),4.03 (s, 2H), 2.86-2.71 (m, 1H), 2.21 (s, 3H), 1.21 (2d, J = 6.7 Hz,6H). 112C F 564 (M + H) 154-158 (CDCl₃) δ 8.58 (s, 1H), 8.32 (s, 1H),8.23 (d, J = 8.4 Hz, 2H), 7.87-7.75 (m, 4H), 7.43-7.33 (m, 4H),7.26-7.19 (m, 2H), 4.02 (s, 2H), 1.86-1.77 (m, 1H), 0.90-0.83 (m, 2H),0.77-0.68 (m, 1H), 0.67-0.59 (m, 1H). 113C F 538 (M + H) 111-116;(Acetone-d₆) δ 9.20 (s, 1H), 8.28 (d, J = 8.2 Hz, 210-212 3H), 8.13 (d,J = 9.0 Hz, 2H), 7.94 (d, J = 8.2 Hz, 2H), 7.60 (d, J = 8.8 Hz, 2H),7.39 (t, J = 17.1 Hz, 4H), 4.15 (q, J = 17.3 Hz, 2H), 2.23 (s, 3H) 114CF 568 (M + H) 203-205 (CDCl₃) δ 8.58 (s, 1H), 8.33 (s, 1H), 8.22 (d, J =8.3 Hz, 2H), 7.88-7.67 (m, 4H), 7.38 (d, J = 8.4 Hz, 2H), 7.14 (d, J =8.3 Hz, 1H), 6.87 (d, J = 8.9 Hz, 2H), 3.98 (s, 2H), 3.83 (s, 3H), 2.20(s, 3H) 115C F 554 (M + H) 261-264 (CDCl₃) δ 8.58 (s, 1H), 8.35 (s, 1H),8.23 (d, J = 8.2 Hz, 2H), 7.82 (m, 4H), 7.40 (d, J = 8.6 Hz, 2H), 7.30(d, 2H), 7.03 (d, J = 8.8 Hz, 2H), 3.97 (s, 2H), 3.86 (s, 3H) 116C F 568(M + H) 92-97 (CDCl₃) δ 8.58 (s, 1H), 8.31 (s, 1H), 8.22 (d, J = 8.3 Hz,2H), 7.88-7.72 (m, 4H), 7.48-7.32 (m, 3H), 7.31-7.20 (m, 1H), 7.13-6.97(m, 2H), 4.09 (q, J = 7.0 Hz, 2H), 3.95 (t, J = 11.7 Hz, 2H), 1.33 (t, J= 7.0 Hz, 3H). 117C F 539 (M + H) 127-132 (CDCl₃) δ 8.59 (s, 1H), 8.54(dd, J = 4.8, 1.3 Hz, 1H), 8.28 (s, 1H), 8.22 (d, J = 8.4 Hz, 2H),7.84-7.77 (m, 4H), 7.77-7.72 (m, 1H), 7.38 (dd, J = 7.7, 5.0 Hz, 3H),4.02 (d, J = 1.2 Hz, 2H), 2.30 (s, 3H) 118C F 539 (M + H) 215 (dec)(CDCl₃) δ 8.67 (s, 1H), 8.59 (s, 1H), 8.24 (d, J = 8.4 Hz, 2H), 7.99 (d,J = 8.4 Hz, 1H), 7.84 (dd, J = 8.3, 3.8 Hz, 4H), 7.80 (s, 1H), 7.42-7.39(m, 3H), 4.03 (d, J = 1.3 Hz, 2H), 2.26 (s, 3H). 119C F 580 (M + H)124-138 (CDCl₃) δ 8.58 (s, 1H), 8.29 (s, 1H), 8.23 (d, J = 8.4 Hz, 2H),7.88-7.77 (m, 4H), 7.48-7.34 (m, 5H), 7.23-7.18 (m, 1H), 4.06-3.93 (m,2H), 2.40 (qd, J = 14.2, 7.3 Hz, 2H), 1.94-1.81 (m, 1H), 0.89 (d, J =6.6 Hz, 6H). 120C F 549.7 (M + H) 153-159 (CDCl₃) δ 8.67 (s, 1H), 8.30(s, 1H), 8.24 (d, J = 8.3 Hz, 2H), 7.92 (d, J = 8.5 Hz, 2H), 7.82 (m,3H), 4.01 (d, J = 1.5 Hz, 2H), 3.80-3.64 (m, 2H), 2.91-2.76 (m, 2H),1.30-1.14 (m, 6H) 121C F 578 (M + H) 143-147; (CDCl₃) δ 8.57 (d, J = 7.4Hz, 1H), 8.30 (s, 148-151 1H), 8.23 (d, J = 8.4 Hz, 2H), 7.87-7.78 (m,4H), 7.49-7.33 (m, 5H), 7.29-7.26 (m, 1H), 6.03 (s, 1H), 3.95 (s, 2H),1.84 (d, J = 1.3 Hz, 3H), 1.71 (d, J = 1.2 Hz, 3H). 122C F 579.3 (M + 1)169-171 (CDCl3) δ 8.58 (s, 1H), 8.24-8.18 (m, 2H), 7.99-7.94 (m, 2H),7.84-7.78 (m, 2H), 7.47 (dd, J = 5.0, 1.1 Hz, 2H), 7.40 (d, J = 8.3 Hz,2H), 7.34 (ddd, J = 7.9, 5.1, 3.7 Hz, 1H), 7.18 (d, J = 7.6 Hz, 1H),4.00 (d, J = 1.5 Hz, 2H), 3.72 (dd, J = 7.0, 5.1 Hz, 2H), 2.94-2.80 (m,1H), 2.22 (s, 3H), 1.23 (m, 9H). 123C F 553 (M + H) 130-135 (CDCl₃) δ8.62 (s, 1H), 8.54 (d, J = 3.2 Hz, 1H), 8.28-8.19 (m, 3H), 7.82 (d, J =8.8 Hz, 5H), 7.43-7.37 (m, 3H), 4.02 (s, 2H), 2.63 (d, J = 7.6 Hz, 2H),1.22 (s, 3H) 124C F 608 (M + H) 140-145 (CDCl₃) δ 8.58 (s, 1H), 8.29 (s,1H), 8.23 (d, J = 8.4 Hz, 2H), 7.89-7.75 (m, 4H), 7.58-7.51 (m, 1H),7.49-7.36 (m, 5H), 4.04 (d, J = 17.4 Hz, 1H), 3.97 (d, J = 17.4 Hz, 1H).125C F 580 (M + H) 130-140 (CDCl₃) δ 8.58 (s, 1H), 8.31 (s, 1H), 8.22(d, J = 8.4 Hz, 2H), 7.86-7.78 (m, 4H), 7.65 (dd, J = 8.1, 1.4 Hz, 1H),7.49-7.42 (m, 1H), 7.40 (d, J = 8.3 Hz, 2H), 7.35 (dt, J = 7.6, 1.5 Hz,1H), 7.05 (dd, J = 7.8, 1.5 Hz, 1H), 3.95 (s, 2H), 1.38 (s, 9H). 126C F590 (M + H) 175-177 (CDCl₃) δ 8.58 (s, 1H), 8.29 (s, 1H), 8.23 (d, J =8.4 Hz, 2H), 7.87-7.77 (m, 4H), 7.52 (ddd, J = 8.1, 6.0, 3.4 Hz, 1H),7.44-7.34 (m, 5H), 6.46 (t, J_(HF) = 73.5 Hz, 1H), 4.05-3.95 (m, 2H).127C F 578 (M + H) 112-115 (CDCl₃) δ 8.58 (s, 1H), 8.32 (s, 1H), 8.22(d, J = 8.3 Hz, 2H), 7.87-7.75 (m, 4H), 7.43-7.32 (m, 4H), 7.26-7.24 (m,2H), 4.23 (q, J = 7.3 Hz, 1H), 1.85-1.78 (m, 4H), 0.90-0.78 (m, 2H),0.78-0.69 (m, 1H), 0.65-0.55 (m, 1H). 128C F 580 (M + H) 164-171 (CDCl₃)δ 8.58 (s, 1H), 8.29 (d, J = 7.8 Hz, 1H), 8.22 (d, J = 8.3 Hz, 2H),7.88-7.74 (m, 4H), 7.48-7.30 (m, 5H), 7.20 (t, J = 11.1 Hz, 1H),4.26-4.14 (m, 1H), 2.50-2.46 (m, 2H), 1.79 (d, J = 7.3 Hz, 3H),1.69-1.56 (m, 2H), 0.93 (t, J = 7.3 Hz, 3H). 129C F 606 (M + H) 140-142(CDCl₃) δ 8.58 (s, 1H), 8.30 (s, 1H), 8.22 (d, J = 8.4 Hz, 2H),7.87-7.76 (m, 4H), 7.53-7.47 (m, 2H), 7.44-7.35 (m, 3H), 4.27 (q, J =7.3 Hz, 1H), 1.82 (d, J = 7.3 Hz, 3H). 130C F 590 (M + H) 93-97; (CDCl₃)δ 8.58 (s, 1H), 8.31 (s, 1H), 191-194 8.22 (d, J = 8.4 Hz, 2H),7.88-7.76 (m, 4H), 7.48-7.34 (m, 4H), 7.20 (tt, J = 12.4, 6.1 Hz, 1H),4.35-4.18 (m, 1H), 1.81 (2d, J = 7.3 Hz, 3H). 131C F 572 (M − H) 93-98;(CDCl₃) δ 8.58 (s, 1H), 8.32 (s, 1H), 185-186 8.26-8.20 (m, 2H),7.86-7.78 (m, 4H), 7.53-7.42 (m, 1H), 7.40 (d, J = 8.3 Hz, 2H), 7.09 (t,J = 8.1 Hz, 2H), 4.26 (q, J = 7.3 Hz, 1H), 1.80 (d, J = 7.3 Hz, 3H).132C J 552 (M + H) 193-196 (CDCl₃) δ 8.56 (s, 1H), 8.22 (s, 1H), 8.17(d, J = 8.4 Hz, 2H), 7.80 (ddd, J = 9.5, 6.9, 4.9 Hz, 4H), 7.43-7.33 (m,4H), 7.31-7.21 (m, 2H), 4.05 (td, J = 9.4, 7.1 Hz, 1H), 3.97-3.87 (m,1H), 3.42-3.33 (m, 1H), 3.33-3.24 (m, 1H), 3.12 (heptet, J = 6.8 Hz,1H), 1.27 (d, J = 6.8 Hz, 3H), 1.22 (d, J = 6.9 Hz, 3H). 133C J 538 (M +H) 167-169 (CDCl₃) δ 8.55 (d, J = 7.1 Hz, 1H), 8.23 (s, 1H), 8.17 (d, J= 8.4 Hz, 2H), 7.80 (dt, J = 11.4, 6.2 Hz, 4H), 7.43-7.23 (m, 6H), 4.00(s, 2H), 3.32 (s, 2H), 2.67 (q, J = 7.6 Hz, 2H), 1.25 (dd, J = 9.6, 5.5Hz, 3H). 134C J 536 (M + H) 217-220; (CDCl₃) δ 8.65 (s, 1H), 8.22 (s,1H), 230-232 8.18 (d, J = 8.4 Hz, 2H), 7.94-7.88 (m, 2H), 7.81-7.78 (m,4H), 7.41 (dd, J = 7.8, 1.5 Hz, 1H), 7.39-7.33 (m, 1H), 7.30-7.24 (m,1H), 7.23 (dd, J = 7.8, 1.5 Hz, 1H), 4.09-4.02 (m, 1H), 3.98-3.88 (m,1H), 3.43-3.24 (m, 2H), 3.12 (heptet, J = 6.9 Hz, 1H), 1.27 (d, J = 6.8Hz, 3H), 1.22 (d, J = 6.9 Hz, 3H). 135C J 566 (M + H) 167-169 (CDCl₃) δ8.56 (s, 1H), 8.19 (dd, J = 12.7, 9.0 Hz, 3H), 7.84-7.74 (m, 4H), 7.37(dd, J = 14.9, 6.1 Hz, 4H), 7.26 (s, 1H), 7.21 (d, J = 7.6 Hz, 1H),4.17-3.85 (m, 2H), 3.42-3.22 (m, 2H), 2.82 (d, J = 23.6 Hz, 1H),1.80-1.55 (m, 2H), 1.23 (2d, J = 6.9 Hz, 3H), 0.82 (2t, J = 7.4 Hz, 3H).136C J 552 (M + H) 143-147 (CDCl₃) δ 8.56 (s, 1H), 8.22 (s, 1H), 8.17(d, J = 8.4 Hz, 2H), 7.84-7.74 (m, 4H), 7.39 (d, J = 8.3 Hz, 2H), 7.24(d, J = 7.5 Hz, 1H), 7.19 (d, J = 6.4 Hz, 1H), 7.15 (d, J = 7.3 Hz, 1H),3.92 (qt, J = 10.1, 7.3 Hz, 2H), 3.43-3.28 (m, 2H), 2.72-2.51 (m, 2H),2.27 (s, 3H), 1.25 (t, J = 7.6 Hz, 3H). 137C J 554 (M + H) 183-186(CDCl₃) δ 8.56 (d, J = 5.3 Hz, 1H), 8.26 (s, 1H), 8.17 (d, J = 8.4 Hz,2H), 7.84-7.74 (m, 4H), 7.39 (d, J = 8.3 Hz, 2H), 7.18 (d, J = 8.5 Hz,1H), 6.81 (dt, J = 8.4, 2.9 Hz, 2H), 3.96 (t, J = 6.6 Hz, 2H), 3.81 (s,3H), 3.30 (t, J = 6.9 Hz, 2H), 2.28 (s, 3H). 138C J 568 (M + H) 231-233(CDCl₃) δ 8.56 (d, J = 5.4 Hz, 1H), 8.25 (s, 1H), 8.17 (d, J = 8.4 Hz,2H), 7.84-7.72 (m, 4H), 7.39 (d, J = 8.3 Hz, 2H), 6.67 (s, 2H),3.92-3.85 (m, 2H), 3.79 (s, 3H), 3.34 (t, J = 7.1 Hz, 2H), 2.25 (s, 6H).139C J 552 (M + H) 195-197 (CDCl₃) δ 8.56 (s, 1H), 8.24 (s, 1H), 8.17(d, J = 8.3 Hz, 2H), 7.83-7.73 (m, 4H), 7.39 (d, J = 8.3 Hz, 2H), 6.95(s, 2H), 3.90 (t, J = 7.1 Hz, 2H), 3.35 (t, J = 7.1 Hz, 2H), 2.30 (s,3H), 2.23 (s, 6H). 140C J 540 (M + H) 181-184 (CDCl₃) δ 8.56 (s, 1H),8.24 (s, 1H), 8.17 (d, J = 8.3 Hz, 2H), 7.84-7.75 (m, 4H), 7.43-7.36 (m,3H), 7.30 (ddd, J = 12.6, 6.9, 3.1 Hz, 1H), 7.06-6.97 (m, 2H), 4.04 (t,J = 7.0 Hz, 2H), 3.86 (s, 3H), 3.29 (t, J = 7.0 Hz, 2H). 141C J 524 (M +H) 173-176 (CDCl₃) δ 8.56 (s, 1H), 8.25 (s, 1H), 8.18 (d, J = 8.4 Hz,2H), 7.83-7.75 (m, 4H), 7.39 (d, J = 8.3 Hz, 2H), 7.34-7.23 (m, 4H),4.01 (t, J = 6.9 Hz, 2H), 3.32 (t, J = 6.9 Hz, 2H), 2.31 (s, 3H). 142C J538 (M + H) 210-213 (CDCl₃) δ 8.56 (s, 1H), 8.23 (s, 1H), 8.17 (d, J =8.4 Hz, 2H), 7.84-7.74 (m, 4H), 7.39 (d, J = 8.3 Hz, 2H), 7.22-7.10 (m,3H), 3.92 (t, J = 7.1 Hz, 2H), 3.36 (t, J = 7.1 Hz, 2H), 2.28 (s, 6H).143C J 562 (M + H) 221-224 (CDCl₃) δ 8.56 (s, 1H), 8.23 (s, 1H), 8.18(d, J = 8.4 Hz, 2H), 7.83-7.74 (m, 4H), 7.38 (d, J = 8.3 Hz, 2H), 7.30(dt, J = 7.4, 4.8 Hz, 2H), 7.15-7.09 (m, 1H), 4.05 (ddd, J = 9.4, 7.3,5.2 Hz, 1H), 4.00-3.89 (m, 1H), 3.46-3.30 (m, 2H). 144C J 586 (M + H)117-123; (300 MHz, CDCl₃) δ 8.56 (d, J = 4.3 Hz, 134-138 1H), 8.34 (s,1H), 8.21 (s, 1H), 8.18 (s, 1H), 7.81 (dd, J = 8.9, 2.3 Hz, 4H), 7.52(d, J = 6.7 Hz, 1H), 7.50-7.31 (m, 10H), 3.53-3.49 (m, 2H), 2.95-2.90(d, J = 6.8 Hz, 2H). 145C J 550 (M + H) 207-209 (CDCl₃) δ 8.56 (s, 1H),8.26 (s, 1H), 8.18 (d, J = 8.3 Hz, 2H), 7.84-7.74 (m, 4H), 7.39 (d, J =8.3 Hz, 2H), 7.32-7.21 (m, 3H), 7.01 (dd, J = 8.9, 2.5 Hz, 1H),4.12-4.04 (s, 2H), 3.34 (t, J = 6.9 Hz, 2H), 2.09-1.98 (m, 1H), 0.95(dd, J = 8.5, 1.7 Hz, 2H), 0.72 (bs, 2H). 146C J 554 (M + H) 141-144(CDCl₃) δ 8.56 (d, J = 5.2 Hz, 1H), 8.24 (s, 1H), 8.17 (d, J = 8.3 Hz,2H), 7.80 (dt, J = 8.2, 4.6 Hz, 4H), 7.45-7.36 (m, 3H), 7.30-7.24 (m,1H), 7.05-6.95 (m, 2H), 4.13-4.02 (m, 4H), 3.28 (t, J = 7.0 Hz, 2H),1.44-1.35 (m, 3H). 147C J 540 (M + H) 168-170 (CDCl₃) δ 8.57 (s, 1H),8.37 (s, 1H), 8.21 (d, J = 8.3 Hz, 2H), 7.87-7.76 (m, 4H), 7.40 (d, J =8.4 Hz, 2H), 7.29 (dd, J = 14.2, 6.0 Hz, 1H), 7.24 (d, J = 2.3 Hz, 1H),7.09-7.02 (m, 1H), 6.72 (dd, J = 8.0, 2.1 Hz, 1H), 4.20 (t, J = 6.9 Hz,2H), 3.83 (d, J = 8.7 Hz, 3H), 3.24 (t, J = 6.9 Hz, 2H). 148C J 546 (M +H) 213-216 (CDCl₃) δ 8.56 (s, 1H), 8.24 (s, 1H), 8.18 (d, J = 8.3 Hz,2H), 7.80 (dt, J = 4.0, 2.5 Hz, 4H), 7.39 (d, J = 8.3 Hz, 2H), 7.30(ddd, J = 8.5, 7.4, 4.2 Hz, 1H), 7.05-6.97 (m, 2H), 4.02 (t, J = 6.9 Hz,2H), 3.36 (t, J = 6.9 Hz, 2H). 149C J 612 (M + H) 200-203 (CDCl₃) δ 8.56(s, 1H), 8.18 (d, J = 2.6 Hz, 2H), 8.16 (s, 1H), 7.80 (dt, J = 8.3, 4.7Hz, 4H), 7.71 (t, J = 8.6 Hz, 2H), 7.47 (t, J = 7.7 Hz, 1H), 7.39 (d, J= 8.3 Hz, 2H), 4.18-4.07 (m, 1H), 3.93-3.84 (m, 1H), 3.46 (td, J = 10.7,7.3 Hz, 1H), 3.35-3.25 (m, 1H). 150C J 566 (M + H) 169-172 (CDCl₃) δ8.56 (s, 1H), 8.22 (s, 1H), 8.17 (d, J = 8.4 Hz, 2H), 7.80 (dt, J =11.5, 6.2 Hz, 4H), 7.39 (d, J = 8.3 Hz, 2H), 7.31-7.27 (m, 3H),7.26-7.24 (m, 1H), 4.10-3.89 (m, 2H), 3.38-3.32 (m, 2H), 2.48 (s, 2H),2.01-1.84 (m, 1H), 0.91 (d, J = 6.2 Hz, 6H). 151C J 564 (M + H) 149-153(CDCl₃) δ 8.57 (s, 1H), 8.25 (s, 1H), 8.18 (d, J = 8.3 Hz, 2H), 7.99 (s,1H), 7.81 (dt, J = 8.3, 4.5 Hz, 4H), 7.39 (dd, J = 6.1, 3.5 Hz, 3H),7.33-7.27 (m, 2H), 6.21 (s, 1H), 3.92 (t, J = 6.9 Hz, 2H), 3.26 (t, J =6.8 Hz, 2H), 1.89 (d, J = 1.1 Hz, 3H), 1.79 (d, J = 1.1 Hz, 3H). 152C J576 (M + H) 161-163 (CDCl₃) δ 8.57 (s, 1H), 8.23-8.16 (m, 3H), 7.83-7.77(m, 4H), 7.48 (dd, J = 7.5, 2.0 Hz, 1H), 7.39 (d, J = 8.3 Hz, 2H), 7.33(dt, J = 7.2, 2.1 Hz, 2H), 7.28 (dd, J = 9.8, 1.9 Hz, 1H), 6.52 (t,J_(HF) = 74.1 Hz, 1H), 4.06 (t, J = 6.9 Hz, 2H), 3.33 (t, J = 6.9 Hz,2H). 153C J 594 (M + H) 195-197 (CDCl₃) δ 8.57 (s, 1H), 8.25 (s, 1H),8.19 (d, J = 8.4 Hz, 2H), 7.81 (dt, J = 4.1, 2.6 Hz, 4H), 7.58-7.52 (m,1H), 7.42-7.33 (m, 5H), 4.05 (t, J = 6.9 Hz, 2H), 3.31 (t, J = 6.9 Hz,2H). 154C J 538 (M + H) 164-167 CDCl₃) δ 8.56 (s, 1H), 8.23 (d, J = 9.8Hz, 1H), 8.17 (d, J = 8.3 Hz, 2H), 7.84-7.74 (m, 4H), 7.39 (d, J = 8.3Hz, 2H), 7.35-7.27 (m, 3H), 7.19 (s, 1H), 3.54-3.31 (m, 1H), 3.07-2.93(m, 1H), 2.31 (d, J = 9.0 Hz, 3H), 1.62-1.56 (m, 1H), 1.31-1.19 (m, 3H).155C J 566 (M + H) 201-204 Two Isomers (CDCl₃) δ 8.56 (s, 2H), 8.18 (dd,J = 10.8, 7.4 Hz, 6H), 7.84-7.73 (m, 8H), 7.45-7.30 (m, 8H), 7.30-7.23(m, 2H), 7.20 (d, J = 6.7 Hz, 1H), 7.12 (dd, J = 7.8, 1.2 Hz, 1H),4.43-4.33 (m, 1H), 4.16 (dd, J = 12.6, 6.3 Hz, 1H), 3.48 (dt, J = 13.3,6.7 Hz, 1H), 3.37 (dd, J = 10.8, 6.2 Hz, 1H), 3.24 (dt, J = 13.7, 6.9Hz, 1H), 3.08-2.92 (m, 3H), 1.33-1.16 (m, 18H). 156C J 566 (M + H)105-110 (CDCl₃) δ 8.56 (s, 1H), 8.20 (d, J = 3.4 Hz, 1H), 8.16 (d, J =8.4 Hz, 2H), 7.84-7.73 (m, 4H), 7.39 (d, J = 8.3 Hz, 2H), 7.25-7.09 (m,3H), 4.39-4.23 (m, 1H), 3.53-3.35 (m, 1H), 3.04-3.00 (m, 1H), 2.78-2.49(m, 2H), 2.28 (2s, 3H), 1.34-1.08 (m, 6H). 157C J 592 (M + H) 175-176(CDCl₃) δ 8.56 (d, J = 0.6 Hz, 1H), 8.21 (s, 1H), 8.17 (d, J = 8.2 Hz,2H), 7.82-7.77 (m, 4H), 7.49-7.35 (m, 4H), 7.30-7.28 (m, 1H), 4.64-4.57(m, 1H), 3.44 (dd, J = 10.2, 6.3 Hz, 1H), 3.16-3.01 (m, 1H), 1.27 (d, J= 6.3 Hz, 3H). 158C J 572 (M + H)  99-102 Two Isomers (CDCl₃) δ 8.56 (s,2H), 8.20 (s, 2H), 8.19-8.12 (m, 4H), 7.84-7.73 (m, 8H), 7.39 (d, J =8.3 Hz, 4H), 7.36-7.29 (m, 2H), 7.25-7.17 (m, 4H), 4.78-4.55 (m, 1H),4.35 (dt, J = 9.4, 6.3 Hz, 1H), 3.48 (dd, J = 10.7, 6.5 Hz, 1H), 3.38(dd, J = 10.7, 6.2 Hz, 1H), 3.11 (dd, J = 10.7, 9.4 Hz, 1H), 3.01 (dd, J= 10.7, 8.3 Hz, 1H), 2.35 (s, 3H), 2.30 (s, 3H), 1.26 (d, J = 6.3 Hz,3H), 1.21 (d, J = 6.4 Hz, 3H) 159C J 607 (M + H)  85 (dec) (CDCl₃) δ8.56 (s, 1H), 8.18 (dd, J = 11.9, 5.3 Hz, 3H), 7.79 (dd, J = 8.7, 6.5Hz, 4H), 7.47 (dd, J = 7.8, 2.3 Hz, 1H), 7.42-7.32 (m, 5H), 4.48-4.29(m, 1H), 3.45 (dd, J = 10.7, 6.4 Hz, 1H), 2.98 (dd, J = 10.7, 7.1 Hz,1H), 1.26 (d, J = 6.3 Hz, 3H) 160C J 626 (M + H)  93 (dec) Two Isomers(CDCl3) δ 8.56 (s, 2H), 8.19-8.12 (m, 6H), 7.84-7.73 (m, 10H), 7.71 (d,J = 8.2 Hz, 2H), 7.47 (t, J = 8.0 Hz, 2H), 7.39 (d, J = 8.3 Hz, 4H),4.76-4.64 (m, 1H), 4.48 (dd, J = 14.6, 6.3 Hz, 1H), 3.43 (dd, J = 10.6,6.2 Hz, 1H), 3.29 (dd, J = 10.5, 5.5 Hz, 1H), 3.16-3.00 (m, 2H), 1.27(d, J = 6.4 Hz, 3H), 1.17 (d, J = 6.4 Hz, 3H) 161C J 566 (M + H) 105(dec) (CDCl₃) δ 8.56 (s, 1H), 8.22 (s, 1H), 8.16 (d, J = 8.4 Hz, 2H),7.83-7.70 (m, 4H), 7.39 (d, J = 8.3 Hz, 2H), 6.94 (d, J = 9.3 Hz, 2H),4.43-4.22 (m, 1H), 3.42 (dd, J = 10.8, 6.5 Hz, 1H), 3.00 (dd, J = 10.8,8.5 Hz, 1H), 2.30 (s, 3H), 2.25 (s, 3H), 2.21 (s, 3H), 1.20 (d, J = 6.3Hz, 3H) 162C J 568 (M + H) 100 (dec) (CDCl₃) δ 8.56 (s, 1H), 8.24 (s,1H), 8.17 (d, J = 8.4 Hz, 2H), 7.83-7.73 (m, 4H), 7.39 (d, J = 8.3 Hz,2H), 7.18-7.09 (m, 1H), 6.86-6.76 (m, 2H), 4.33-4.19 (m, 1H), 3.82 (s,3H), 3.47-3.38 (m, 1H), 3.00-2.99 (m, 1H), 2.29-2.27 (m, 3H), 1.33-1.15(m, 3H) 163C J 580 (M + H)  92-102 (CDCl₃) δ 8.56 (s, 2H), 8.18 (dd, J =10.7, 5.3 Hz, 6H), 7.84-7.74 (m, 8H), 7.42-7.30 (m, 8H), 7.23-7.10 (m,2H), 4.37 (dd, J = 19.5, 13.6 Hz, 1H), 4.16 (dd, J = 13.1, 6.6 Hz, 1H),3.56-3.42 (m, 1H), 3.34 (dd, J = 10.8, 6.0 Hz, 1H), 3.08-2.87 (m, 3H),2.70 (dd, J = 16.0, 7.0 Hz, 1H), 1.71-1.56 (m, 4H), 1.34-1.25 (m, 6H),1.24-1.14 (m, 6H), 0.93-0.73 (m, 6H) 164C J 589 (M + H)  80 (dec)(CDCl₃) δ 8.56 (s, 1H), 8.22-8.14 (m, 3H), 7.84-7.76 (m, 4H), 7.42-7.27(m, 6H), 6.51 (t, J_(HF) = 74.3 Hz, 1H), 4.52-4.31 (m, 1H), 3.44 (dd, J= 10.8, 6.5 Hz, 1H), 2.99 (dd, J = 10.8, 7.6 Hz, 1H), 1.25 (d, J = 6.3Hz, 3H) 165C J 580 (M + H) 143 (dec) Two Isomers (CDCl₃) δ 8.56 (s, 2H),8.22 (s, 1H), 8.20 (s, 1H), 8.16 (d, J = 8.3 Hz, 4H), 7.84-7.74 (m, 8H),7.58 (ddd, J = 9.7, 8.0, 1.7 Hz, 2H), 7.39 (d, J = 8.4 Hz, 4H),7.36-7.27 (m, 4H), 7.15 (dd, J = 7.7, 1.6 Hz, 1H), 7.09 (dd, J = 7.6,1.7 Hz, 1H), 4.38-4.22 (m, 2H), 3.61 (dd, J = 10.8, 7.0 Hz, 1H), 3.24(dd, J = 10.7, 5.6 Hz, 1H), 3.07-2.94 (m, 1H), 2.91 (dd, J = 10.8, 1.5Hz, 1H), 1.47-1.38 (m, 24H) 166C J 552 (M + H)  93 (dec) (CDCl₃) δ 8.56(s, 1H), 8.21 (s, 1H), 8.16 (d, J = 8.4 Hz, 2H), 7.84-7.73 (m, 4H), 7.39(d, J = 8.3 Hz, 2H), 7.32-7.28 (m, 3H), 7.20 (s, 1H), 4.20-4.06 (m, 1H),3.41 (s, 1H), 3.05 (dd, J = 10.8, 8.2 Hz, 1H), 2.31-32.30 (m, 3H), 1.66(s, 2H), 0.90-0.88 (m, 3H) 167C J 586 (M + H) 105 (dec) Two Isomers(CDCl₃) δ 8.56 (s, 2H), 8.20 (s, 2H), 8.16 (d, J = 8.3 Hz, 4H),7.83-7.74 (m, 8H), 7.43-7.28 (m, 6H), 7.21 (dd, J = 5.4, 3.3 Hz, 4H),4.49-4.36 (m, 1H), 4.17-4.05 (m, 1H), 3.49 (dd, J = 10.7, 6.6 Hz, 1H),3.40 (dd, J = 10.7, 6.3 Hz, 1H), 3.10 (dd, J = 10.7, 9.4 Hz, 1H), 3.04(dd, J = 10.8, 8.2 Hz, 1H), 2.34 (s, 3H), 2.30 (s, 3H), 1.73-1.48 (m,4H), 0.91 (m, 6H) 168C J 560 (M + H) 199-200 (CDCl₃) δ 8.56 (s, 1H),8.18 (m,, 2H), 7.79 (m, 4H), 7.47 (dd, J = 7.8, 2.3 Hz, 1H), 7.42-7.32(m, 5H), 4.48-4.29 (m, 1H), 3.45 (dd, J = 10.7, 6.4 Hz, 1H), 2.98 (dd, J= 10.7, 7.1 Hz, 1H), 1.26 (d, J = 6.3 Hz, 3H) 169C G 623 (M + H) Oil(CDCl₃) δ 10.45 (s, 1H), 8.59 (s, 1H), 8.25 (d, J = 8.3 Hz, 2H), 7.88(d, J = 8.3 Hz, 2H), 7.81 (d, J = 8.9 Hz, 2H), 7.61 (t, J = 7.5 Hz, 2H),7.40 (d, J = 8.7 Hz, 2H), 7.11 (t, J = 8.0 Hz, 1H), 5.71 (d, J = 1.1 Hz,1H), 2.35 (s, 3H) ¹⁹F NMR (376 MHz, CDCl₃) δ −58.02, −62.31 170C G 606(M + H) 157-159 (CDCl₃) δ 8.56 (s, 1H), 8.19-8.14 (m, 3H), 7.79 (m, 4H),7.56-7.46 (m, 2H), 7.46-7.43 (m, 2H), 7.39 (d, J = 8.3 Hz, 2H), 5.88 (d,J = 1.3 Hz, 1H), 1.86 (d, J = 1.2 Hz, 3H) 171C G 558 (M + H) 236-237(CDCl₃) δ 8.56 (s, 1H), 8.19 (d, J = 5.9 Hz, 2H), 8.16 (s, 1H),7.83-7.76 (m, 4H), 7.45 (tt, J = 8.4, 6.1 Hz, 1H), 7.39 (d, J = 8.3 Hz,2H), 7.10 (dd, J = 8.5, 7.3 Hz, 2H), 5.90 (d, J = 1.3 Hz, 1H), 1.92 (s,3H) 172C G 580 (M + H) 103-108 (CDCl₃) δ 8.56 (d, J = 3.7 Hz, 1H), 8.21(s, 1H), 8.16 (d, J = 8.4 Hz, 2H), 7.84-7.72 (m, 4H), 7.39 (d, J = 8.3Hz, 2H), 6.72 (s, 2H), 5.89 (d, J = 1.3 Hz, 1H), 3.82 (s, 3H), 2.14 (s,6H), 1.75 (d, J = 1.2 Hz, 3H). 173C G 536 (M + H)  87 (dec) (CDCl₃) δ8.56 (s, 1H), 8.19-8.15 (m, 3H), 7.82-7.75 (m, 4H), 7.43-7.30 (m, 5H),7.24 (d, J = 7.3 Hz, 1H), 5.88 (s, 1H), 2.21 (s, 3H), 1.80 (d, J = 1.2Hz, 3H) 174C G 570 (M + H)  95 (dec) (CDCl₃) δ 8.56 (s, 1H), 8.20-8.12(m, 3H), 7.83-7.74 (m, 4H), 7.43-7.36 (m, 3H), 7.32 (t, J = 7.7 Hz, 1H),7.29-7.27 (m, 1H), 5.92 (d, J = 1.3 Hz, 1H), 2.26 (s, 3H), 1.81 (d, J =1.2 Hz, 3H) 175C G 550 (M + H) 132-136 (CDCl₃) δ 8.56 (d, J = 5.0 Hz,1H), 8.21-8.13 (m, 3H), 7.83-7.74 (m, 4H), 7.39 (d, J = 8.2 Hz, 2H),7.29-7.23 (m, 1H), 7.19 (d, J = 7.7 Hz, 2H), 5.92 (d, J = 1.3 Hz, 1H),2.18 (s, 6H), 1.75 (d, J = 1.2 Hz, 3H). 176C G 564 (M + H) 123-138(CDCl₃) δ 8.56 (s, 1H), 8.19-8.14 (m, 3H), 7.83-7.75 (m, 4H), 7.49-7.43(m, 2H), 7.39 (d, J = 8.3 Hz, 2H), 7.33 (ddd, J = 7.8, 5.9, 3.0 Hz, 1H),7.19-7.17 (m, 1H), 5.88 (d, J = 1.3 Hz, 1H), 2.96-2.76 (m, 1H), 1.81 (d,J = 1.2 Hz, 3H), 1.24 (t, J = 6.4 Hz, 3H), 1.22-1.16 (m, 3H). 177C J 566(M + H) 185-187 (CDCl₃) δ 8.55 (s, 1H), 8.14 (d, J = 8.4 Hz, 2H), 8.05(s, 1H), 7.84-7.77 (m, 2H), 7.74 (d, J = 8.3 Hz, 2H), 7.42-7.35 (m, 3H),7.32 (dd, J = 10.6, 4.3 Hz, 1H), 7.28-7.24 (m, 1H), 7.18 (dd, J = 7.8,1.4 Hz, 1H), 3.80-3.69 (m, 1H), 3.59-3.48 (m, 1H), 3.11 (dd, J = 13.2,6.8 Hz, 3H), 2.41-2.27 (m, 2H), 1.22 (t, J = 5.6 Hz, 6H). 178C J 580(M + H) 186-190 (CDCl₃) δ 8.55 (d, J = 3.6 Hz, 1H), 8.14 (d, J = 8.4 Hz,2H), 8.06 (s, 1H), 7.84-7.77 (m, 2H), 7.74 (d, J = 8.4 Hz, 2H), 7.38 (d,J = 9.0 Hz, 3H), 7.32 (td, J = 7.5, 1.4 Hz, 1H), 7.26 (s, 1H), 7.17 (t,J = 7.1 Hz, 1H), 3.69-3.26 (m, 1H), 3.55-3.37 (m, 1H), 3.18-2.98 (m,2H), 2.93-2.80 (m, 1H), 2.47 (d, J = 35.9 Hz, 1H), 1.31-1.12 (m, 9H).179C J 550 (M + H) 212-213 (CDCl₃) δ 8.64 (s, 1H), 8.15 (d, J = 8.4 Hz,2H), 8.06 (s, 1H), 7.91 (d, J = 8.5 Hz, 2H), 7.79 (d, J = 8.6 Hz, 2H),7.75 (d, J = 8.4 Hz, 2H), 7.38 (dd, J = 7.8, 1.6 Hz, 1H), 7.33 (td, J =7.5, 1.4 Hz, 1H), 7.29-7.23 (m, 1H), 7.18 (dd, J = 7.8, 1.4 Hz, 1H),3.78-3.72 (m, 1H), 3.59-3.48 (m, 1H), 3.18-3.04 (m, 3H), 2.40-2.30 (m,2H), 1.26-1.20 (m, 6H). 180C J 566 (M + H) 127-133 (300 MHz, CDCl₃) δ8.55 (s, 1H), 8.13 (d, J = 8.3 Hz, 2H), 8.05 (s, 1H), 7.76 (dd, J =17.0, 8.7 Hz, 4H), 7.37 (t, J = 8.4 Hz, 2H), 7.18 (dd, J = 12.7, 9.6 Hz,3H), 3.54-3.49 (m, 2H), 3.12-3.08 (m, 2H), 2.70-2.55 (m, 2H), 2.39-2.31(m, 2H), 2.28 (s, 3H), 1.25 (t, J = 7.6 Hz, 3H). 181C J 582 (M + H)170-174 (CDCl₃) δ 8.55 (s, 1H), 8.14 (d, J = 8.3 Hz, 2H), 8.08 (s, 1H),7.84-7.76 (m, 2H), 7.74 (d, J = 8.3 Hz, 2H), 7.38 (d, J = 8.3 Hz, 2H),6.65 (s, 2H), 3.79 (s, 3H), 3.52-3.45 (m, 2H), 3.10-3.07 (m, 2H),2.38-2.31 (d, J = 5.7 Hz, 2H), 2.25 (s, 6H). 182C J 552 (M + H) 148-155;(300 MHz, CDCl₃) δ 8.55 (d, J = 1.0 Hz, 166-168 1H), 8.14 (d, J = 8.4Hz, 2H), 8.05 (s, 1H), 7.83-7.76 (m, 2H), 7.74 (d, J = 8.4 Hz, 2H), 7.38(d, J = 9.0 Hz, 2H), 7.14-7.09 (m, 3H), 3.51 (dd, J = 9.1, 3.5 Hz, 2H),3.15-3.03 (m, 2H), 2.36 (s, 2H), 2.28 (s, 6H). 183C J 580 (M + H)159-162 (CDCl₃) δ 8.55 (d, J = 3.7 Hz, 1H), 8.14 (d, J = 8.4 Hz, 2H),8.03 (d, J = 19.3 Hz, 1H), 7.84-7.77 (m, 2H), 7.74 (d, J = 8.4 Hz, 2H),7.38 (d, J = 8.3 Hz, 2H), 7.32 (d, J = 3.8 Hz, 2H), 7.25 (d, J = 6.6 Hz,1H), 7.19 (t, J = 8.0 Hz, 1H), 3.76 (ddd, J = 24.2, 12.0, 5.9 Hz, 1H),3.58-3.46 (m, 1H), 3.11 (dd, J = 15.3, 6.1 Hz, 2H), 2.82 (dd, J = 14.6,7.2 Hz, 1H), 2.41-2.29 (m, 2H), 1.71-1.55 (m, 2H), 1.20 (d, J = 6.8 Hz,3H), 0.87-0.76 (m, 3H). 184C J 566 (M + H) 194-198 (CDCl₃) δ 8.55 (s,1H), 8.14 (d, J = 8.4 Hz, 2H), 8.07 (s, 1H), 7.83-7.76 (m, 2H), 7.74 (d,J = 8.4 Hz, 2H), 7.40 (t, J = 10.1 Hz, 2H), 6.93 (s, 2H), 3.53-3.47 (m,2H), 3.12-3.05 (m, 2H), 2.34 (dt, J = 11.7, 5.8 Hz, 2H), 2.30 (s, 3H),2.23 (s, 6H). 185C J 552 (M + H) 157-160 (CDCl₃) δ 8.55 (s, 1H), 8.14(d, J = 8.4 Hz, 2H), 8.06 (s, 1H), 7.83-7.77 (m, 2H), 7.74 (d, J = 8.3Hz, 2H), 7.38 (d, J = 8.3 Hz, 2H), 7.36-7.27 (m, 3H), 7.23-7.19 (m, 1H),3.74 (m, 1H), 3.50 (m, 1H), 3.10 (d, J = 5.9 Hz, 2H), 2.64 (q, J = 7.6Hz, 2H), 2.40-2.29 (m, 2H), 1.28-1.21 (m, 3H). 186C J 564 (M + H)173-177 (CDCl₃) δ 8.55 (s, 1H), 8.14 (d, J = 8.4 Hz, 2H), 8.09 (s, 1H),7.83-7.77 (m, 2H), 7.81-7.77 (m, 2H), 7.38 (d, J = 8.3 Hz, 2H),7.24-7.22 (m, 3H), 7.05-6.95 (m, 1H), 3.77-3.63 (m, 2H), 3.14-3.07 (m,2H), 2.45-2.29 (m, 2H), 2.09-1.92 (m, 1H), 0.97-0.82 (m, 3H), 0.53 (bs,1H). 187C J 593 (M + H) 180-182 (300 MHz, CDCl₃) δ 8.55 (s, 1H), 8.14(d, J = 8.4 Hz, 2H), 8.05 (d, J = 4.9 Hz, 1H), 7.77 (dd, J = 11.4, 8.6Hz, 4H), 7.39 (t, J = 8.1 Hz, 4H), 7.21 (dd, J = 13.2, 5.6 Hz, 1H),3.65-3.58 (m, 2H), 3.09 (t, J = 5.5 Hz, 2H), 2.45-2.35 (m, 2H). 188C J576 (M + H) 209-212 (CDCl₃) δ 8.56 (s, 1H), 8.15 (d, J = 8.4 Hz, 2H),8.07 (s, 1H), 7.79 (ddd, J = 15.8, 7.8, 5.8 Hz, 4H), 7.38 (d, J = 8.3Hz, 2H), 7.31-7.21 (m, 2H), 7.10 (ddd, J = 9.7, 7.8, 2.0 Hz, 1H), 3.64(t, J = 5.4 Hz, 2H), 3.11 (t, J = 6.0 Hz, 2H), 2.46-2.33 (m, 2H). 189C J560 (M + H) 217-219 (CDCl₃) δ 8.56 (s, 1H), 8.15 (d, J = 8.4 Hz, 2H),8.08 (s, 1H), 7.83-7.74 (m, 4H), 7.38 (d, J = 8.3 Hz, 2H), 7.31-7.21 (m,1H), 7.03-6.94 (m, 2H), 3.72-3.62 (m, 2H), 3.15-3.07 (m, 2H), 2.40-2.34(m, 2H). 190C J 626 (M + H) 190-193 (CDCl₃) δ 8.55 (s, 1H), 8.14 (d, J =8.3 Hz, 2H), 8.00 (s, 1H), 7.83-7.73 (m, 4H), 7.71 (d, J = 8.1 Hz, 1H),7.67 (d, J = 7.7 Hz, 1H), 7.40 (dd, J = 15.8, 8.2 Hz, 3H), 3.79-3.69 (m,1H), 3.55-3.49 (m, 1H), 3.16-3.04 (m, 2H), 2.47-2.31 (m, 2H). 191C J 554(M + H) 150-155 (CDCl₃) δ 8.54 (d, J = 4.3 Hz, 1H), 8.13 (d, J = 8.3 Hz,2H), 8.05 (d, J = 6.3 Hz, 1H), 7.77 (dd, J = 15.4, 8.7 Hz, 4H), 7.38 (d,J = 8.3 Hz, 2H), 7.29 (dd, J = 8.0, 4.8 Hz, 2H), 7.04-6.93 (m, 2H), 3.85(s, 3H), 3.65-3.61 (m, 2H), 3.10-3.06 (m, 2H), 2.36-2.28 (s, 2H). 192C J568 (M + H) 164-167; (CDCl₃) δ 8.55 (s, 1H), 8.14 (d, J = 8.4 Hz,168-173 2H), 8.09 (s, 1H), 7.82-7.77 (m, 2H), 7.74 (d, J = 6.7 Hz, 2H),7.38 (d, J = 8.3 Hz, 2H), 7.13 (d, J = 8.3 Hz, 1H), 6.79 (dd, J = 11.9,3.3 Hz, 2H), 3.81 (s, 3H), 3.74-3.66 (m, 1H), 3.57-3.48 (m, 1H),3.12-3.04 (m, 2H), 2.36-2.30 (m, 2H), 2.25 (s, 3H). 193C J 580 (M + H)155-158 (CDCl₃) δ 8.55 (s, 1H), 8.14 (d, J = 8.4 Hz, 2H), 8.04 (s, 1H),7.83-7.77 (m, 2H), 7.74 (d, J = 8.4 Hz, 2H), 7.38 (d, J = 8.3 Hz, 2H),7.31-7.24 (m, 3H), 7.23-7.20 (m, 1H), 3.82-3.71 (m, 1H), 3.56-3.47 (m,1H), 3.17-3.02 (m, 2H), 2.46 (t, J = 6.7 Hz, 2H), 2.39-2.27 (m, 2H),1.99 (heptet, J = 6.8 Hz, 1H), 0.95-0.92 (m, 6H). 194C J 600 (M + H)102-108 (CDCl₃) δ 8.56 (s, 1H), 8.17 (m 3H), 7.80 (m, 4H), 7.52-7.47 (m,2H), 7.47-7.31 (m, 9H), 3.42-3.05 (m, 2H), 2.86 (bs, 2H), 2.04-1.71 (m,2H). 195C J 538 (M + H) 159-162 (CDCl₃) δ 8.55 (s, 1H), 8.14 (d, J = 8.3Hz, 2H), 8.08 (s, 1H), 7.84-7.77 (m, 2H), 7.75 (d, J = 8.4 Hz, 2H), 7.38(d, J = 8.5 Hz, 2H), 7.31-7.19 (m, 4H), 3.81-3.47 (m, 2H), 3.20-3.00 (m,2H), 2.35 (dt, J = 11.7, 5.8 Hz, 2H), 2.28 (s, 3H). 196C J 572 (M + H)140-143 (CDCl₃) δ 8.55 (s, 1H), 8.14 (d, J = 8.1 Hz, 2H), 8.05 (s, 1H),7.80 (d, J = 8.9 Hz, 2H), 7.75 (d, J = 8.2 Hz, 2H), 7.38 (d, J = 8.8 Hz,2H), 7.33 (dd, J = 6.1, 3.4 Hz, 1H), 7.21-7.15 (m, 2H), 3.72-3.66 (m,1H), 3.55-3.41 (m, 1H), 3.16-3.05 (m, 2H), 2.48-2.34 (m, 2H), 2.32 (s,3H). 197C J 578 (M + H) 151-155 (CDCl₃) δ 8.55 (s, 1H), 8.14 (d, J = 8.2Hz, 2H), 8.06 (s, 1H), 7.80 (d, J = 8.9 Hz, 2H), 7.75 (d, J = 8.2 Hz,2H), 7.38 (d, J = 8.8 Hz, 2H), 7.29 (dd, J = 10.7, 4.6 Hz, 4H), 6.20 (s,1H), 3.59-3.48 (m, 2H), 3.10-3.01 (m, 2H), 2.34-2.20 (m, 2H), 1.90 (s,3H), 1.78 (s, 3H). 198C J 539 (M + H) 186-189 (CDCl₃) δ 8.56 (s, 1H),8.36 (dd, J = 4.8, 1.3 Hz, 1H), 8.15 (d, J = 8.3 Hz, 2H), 8.09 (s, 1H),7.78 (m, 4H), 7.54 (dd, J = 7.5, 0.9 Hz, 1H), 7.37 (d, J = 8.5 Hz, 2H),7.13 (dd, J = 7.4, 4.8 Hz, 1H), 3.87 (t, J = 5.7 Hz, 2H), 3.12-3.03 (m,2H), 2.40-2.32 (m, 2H), 2.24 (s, 3H). 199C J 608 (M + H) 207-208 (CDCl₃)δ 8.55 (s, 1H), 8.15 (d, J = 8.4 Hz, 2H), 8.05 (s, 1H), 7.83-7.78 (m,2H), 7.76 (d, J = 8.4 Hz, 2H), 7.43-7.36 (m, 3H), 7.34 (t, J = 4.7 Hz,3H), 3.71-3.64 (m, 2H), 3.12-3.06 (m, 2H), 2.39-2.30 (m, 2H). 200C J 590(M + H) 170-172 (CDCl₃) δ 8.56 (s, 1H), 8.15 (d, J = 8.4 Hz, 2H), 8.03(s, 1H), 7.83-7.77 (m, 2H), 7.76 (d, J = 8.3 Hz, 2H), 7.42-7.27 (m, 6H),6.74-6.29 (m, 1H), 3.70-3.64 (m, 2H), 3.13-3.06 (m, 2H), 2.40-2.31 (m,2H). 201C J 626 (M + H) 190-193 (CDCl₃) δ 8.55 (s, 1H), 8.14 (d, J = 8.3Hz, 2H), 8.00 (s, 1H), 7.83-7.73 (m, 4H), 7.71 (d, J = 8.1 Hz, 1H), 7.67(d, J = 7.7 Hz, 1H), 7.40 (dd, J = 15.8, 8.2 Hz, 3H), 3.79-3.69 (m, 1H),3.55-3.49 (m, 1H), 3.16-3.04 (m, 2H), 2.47-2.31 (m, 2H). 202C J 554 (M +H) 231-234 (CDCl₃) δ 8.56 (s, 1H), 8.19-8.08 (m, 3H), 7.84-7.72 (m, 4H),7.39 (d, J = 8.4 Hz, 2H), 7.25-7.20 (m, 2H), 6.96-6.88 (m, 2H), 3.83 (s,3H), 3.76-3.68 (m, 2H), 3.13-3.03 (m, 2H), 2.39-2.27 (m, 2H). 203C J 631(M + H) 200-201 (CDCl₃) δ 8.56 (s, 1H), 8.15 (d, J = 8.2 Hz, 2H), 8.06(s, 1H), 7.83-7.77 (m, 2H), 7.75 (d, J = 8.2 Hz, 2H), 7.39 (d, J = 8.5Hz, 2H), 7.28-7.25 (m, 2H), 3.51-3.42 (m, 2H), 3.14-3.05 (m, 2H), 2.35(s, 2H), 2.25 (s, 6H). 204C J 568 (M + H) 193-196 (CDCl₃) δ 8.55 (s,1H), 8.14 (d, J = 8.4 Hz, 2H), 8.09 (s, 1H), 7.84-7.77 (m, 2H), 7.75 (d,J = 8.4 Hz, 2H), 7.38 (d, J = 8.3 Hz, 2H), 7.08 (t, J = 4.0 Hz, 2H),6.88 (d, J = 8.6 Hz, 1H), 3.82 (s, 3H), 3.66-3.58 (m, 2H), 3.11-3.03 (m,2H), 2.36-2.27 (m, 5H). 205C J 539 (M + H) Oil (CDCl₃) δ 8.55 (s, 1H),8.45 (dd, J = 4.8, 1.6 Hz, 1H), 8.18-8.12 (m, 2H), 8.06 (s, 1H),7.82-7.72 (m, 4H), 7.53 (dd, J = 7.9, 1.6 Hz, 1H), 7.40-7.33 (m, 2H),7.24-7.18 (m, 1H), 3.63 (br s, 2H), 3.18-3.03 (m, 2H), 2.51 (s 3H), 2.35(dt, J = 11.7, 5.7 Hz, 2H) 206C J 554 (M + H) 177-178 (CDCl₃) δ 8.56 (s,1H), 8.16 (d, J = 8.9 Hz, 3H), 7.84-7.73 (m, 4H), 7.39 (d, J = 8.8 Hz,2H), 7.30 (t, J = 8.1 Hz, 1H), 6.95-6.85 (m, 2H), 6.78 (dt, J = 11.1,5.5 Hz, 1H), 3.81 (s, 3H), 3.79-3.73 (m, 2H), 3.12-3.04 (m, 2H),2.38-2.28 (m, 2H). 207C J 596 (M + H) 171-173 (CDCl₃) δ 8.57 (s, 1H),8.23-8.13 (m, 3H), 8.06 (d, J = 8.5 Hz, 2H), 7.80 (dd, J = 8.5, 4.5 Hz,4H), 7.39 (d, J = 8.5 Hz, 4H), 4.38 (q, J = 7.2 Hz, 2H), 3.82 (t, J =6.0 Hz, 2H), 3.14-3.03 (m, 2H), 2.37 (s, 2H), 1.40 (t, J = 7.1 Hz, 3H).208C J 568 (M + H) 171-173 (CDCl₃) δ 8.55 (s, 1H), 8.14 (d, J = 8.3 Hz,2H), 8.07 (s, 1H), 7.84-7.77 (m, 2H), 7.75 (d, J = 8.3 Hz, 2H), 7.38 (d,J = 8.3 Hz, 2H), 7.32-7.23 (m, 2H), 6.99 (ddd, J = 8.3, 5.5, 1.4 Hz,2H), 4.08 (q, J = 7.0 Hz, 2H), 3.69-3.57 (m, 2H), 3.16-3.02 (m, 2H),2.32 (dt, J = 11.7, 5.9 Hz, 2H), 1.39 (t, J = 7.0 Hz, 3H). 209C J 550(M + H) 212-213 (CDCl₃) δ 8.64 (s, 1H), 8.15 (d, J = 8.4 Hz, 2H), 8.06(s, 1H), 7.91 (d, J = 8.5 Hz, 2H), 7.79 (d, J = 8.6 Hz, 2H), 7.75 (d, J= 8.4 Hz, 2H), 7.38 (dd, J = 7.8, 1.6 Hz, 1H), 7.33 (td, J = 7.5, 1.4Hz, 1H), 7.29-7.23 (m, 1H), 7.18 (dd, J = 7.8, 1.4 Hz, 1H), 3.78-3.72(m, 1H), 3.59-3.48 (m, 1H), 3.18-3.04 (m, 3H), 2.40-2.30 (m, 2H),1.26-1.20 (m, 6H). 210C J 580 (M + H) 136-139 (CDCl₃) δ 8.55 (s, 1H),8.14 (d, J = 8.4 Hz, 2H), 8.07 (s, 1H), 7.83-7.77 (m, 2H), 7.75 (d, J =8.4 Hz, 2H), 7.55-7.49 (m, 1H), 7.38 (d, J = 8.3 Hz, 2H), 7.32-7.26 (m,2H), 7.19-7.13 (m, 1H), 3.72 (ddd, J = 12.9, 9.3, 3.8 Hz, 1H), 3.60-3.51(m, 1H), 3.15 (ddd, J = 13.3, 9.4, 4.0 Hz, 1H), 3.10-3.01 (m, 1H),2.51-2.36 (m, 1H), 2.36-2.22 (m, 1H), 1.43 (s, 9H). 211C J 566 (M + H)100-106 (CDCl₃) δ 8.55 (s, 1H), 8.15 (d, J = 8.4 Hz, 2H), 8.10 (s, 1H),7.79 (dt, J = 10.4, 5.8 Hz, 4H), 7.38 (d, J = 8.3 Hz, 2H), 7.11 (s, 3H),3.85-3.78 (m, 2H), 3.20-3.12 (m, 2H), 2.30 (s, 6H), 2.13-2.07 (m, 2H),1.87-1.82 (m, 2H). 212C J 580 (M + H) 186-188 (CDCl₃) δ 8.55 (s, 1H),8.19-8.10 (m, 3H), 7.79 (dt, J = 10.7, 5.9 Hz, 4H), 7.38 (dd, J = 8.5,2.6 Hz, 3H), 7.30 (td, J = 7.5, 1.4 Hz, 1H), 7.23 (td, J = 7.5, 1.7 Hz,1H), 7.13 (dd, J = 7.8, 1.4 Hz, 1H), 3.94 (bs, 2H), 3.24-3.02 (m, 3H),2.13-2.05 (m, 2H), 1.84-1.73 (m, 2H), 1.24 (t, J = 10.5 Hz, 6H). 213C J580 (M + H) 123-127 (CDCl₃) δ 8.55 (s, 1H), 8.13 (d, J = 8.4 Hz, 2H),8.03 (d, J = 4.4 Hz, 1H), 7.83-7.76 (m, 2H), 7.74 (d, J = 8.0 Hz, 2H),7.38 (d, J = 8.4 Hz, 2H), 7.24-7.15 (m, 2H), 7.12 (dd, J = 11.9, 4.6 Hz,1H), 3.82-3.71 (m, 1H), 3.30-3.18 (m, 1H), 3.07-2.94 (m, 1H), 2.72-2.40(m, 3H), 2.30-2.16 (m, 4H), 1.30-1.12 (m, 6H). 214C J 622 (M + H)160-162 (CDCl₃) δ 8.55 (s, 1H), 8.15 (d, J = 8.4 Hz, 2H), 8.06 (s, 1H),7.83-7.72 (m, 4H), 7.38 (m, 3H), 7.34 (dd, J = 2.9, 1.5 Hz, 3H), 3.58(ddd, J = 12.3, 3.9, 1.4 Hz, 1H), 3.39 (dd, J = 12.2, 9.2 Hz, 1H), 3.04(ddd, J = 12.2, 3.9, 1.4 Hz, 1H), 2.84 (dd, J = 12.2, 9.5 Hz, 1H),2.61-2.42 (m, 1H), 1.18 (d, J = 6.7 Hz, 3H) 215C J 640 (M + H) 116 (dec)(CDCl₃) δ 8.55 (s, 1H), 8.14 (dd, J = 8.3, 1.5 Hz, 2H), 8.00 (d, J = 4.0Hz, 1H), 7.84-7.72 (m, 4H), 7.72-7.63 (m, 2H), 7.45-7.32 (m, 3H),3.60-3.44 (m, 1H), 3.37-3.27 (m, 1H), 3.03-2.92 (m, 1H), 2.92-2.82 (m,1H), 2.69-2.54 (m, 1H), 1.19-1.12 (m, 3H) 216C J 622 (M + H) 132-135(CDCl₃) δ 8.55 (s, 1H), 8.14 (d, J = 8.4 Hz, 2H), 8.02 (s, 1H),7.82-7.71 (m, 4H), 7.44-7.30 (m, 6H), 3.87 (d, J = 6.3 Hz, 1H), 3.23(td, J = 11.9, 3.8 Hz, 1H), 3.07-2.94 (m, 1H), 2.54-2.43 (m, 1H), 2.19(ddd, J = 13.9, 9.0, 5.0 Hz, 1H), 1.31 (d, J = 6.6 Hz, 3H) 217C J 640(M + H)  93 (dec) Two isomers (CDCl₃) δ 8.55 (s, 2H), 8.14 (dd, J = 8.4,2.7 Hz, 4H), 7.98 (d, J = 4.2 Hz, 2H), 7.83-7.72 (m, 8H), 7.67 (dt, J =12.9, 7.4 Hz, 4H), 7.40 (dd, J = 15.3, 8.1 Hz, 6H), 4.17 (s, 1H), 3.96(td, J = 6.6, 3.1 Hz, 1H), 3.24-3.12 (m, 2H), 3.12-3.01 (m, 2H), 2.41(dddd, J = 10.8, 10.0, 8.9, 4.2 Hz, 2H), 2.30-2.15 (m, 2H), 1.24 (d, J =6.7 Hz, 3H), 1.04 (d, J = 6.7 Hz, 3H) 218C J 580 (M + H)  95 (dec)(CDCl₃) δ 8.55 (s, 1H), 8.18-8.10 (m, 2H), 8.05 (s, 1H), 7.83-7.76 (m,2H), 7.73 (d, J = 8.4 Hz, 2H), 7.41-7.37 (m, 2H), 6.93 (d, J = 9.4 Hz,2H), 3.76 (dd, J = 10.8, 4.6 Hz, 1H), 3.29-3.16 (m, 1H), 2.99 (ddd, J =12.2, 5.9, 3.9 Hz, 1H), 2.54-2.37 (m, 1H), 2.31 (s, 3H), 2.22 (d, J =6.4 Hz, 7H), 1.19 (d, J = 6.7 Hz, 3H) 219C J 592 (M + H) 100 (dec)(CDCl₃) δ 8.55 (s, 1H), 8.14-8.06 (m, 3H), 7.91-7.65 (m, 4H), 7.44-7.37(m, 2H), 7.16-7.09 (m, 1H), 6.93-6.77 (m, 2H), 4.06-3.64 (m, 4H),3.31-3.16 (m, 1H), 3.02-2.92 (m, 1H), 2.51-2.40 (m, 1H), 2.25-2.17 (m,4H), 1.41-1.14 (m, 3H) 220C J 593 (M + H)  95 (dec) Two isomers: (CDCl₃)δ 8.55 (s, 1H), 8.16-8.09 (m, 2H), 8.01 (m, 1H), 7.86-7.76 (m, 2H),7.76-7.70 (m, 2H), 7.64-7.28 (m, 4H), 7.24-7.14 (m, 2H), 4.08-3.65 (m,1H), 3.37-3.15 (m, 1H), 3.09-2.92 (m, 1H), 2.80 (td, J = 14.2, 6.8 Hz,1H), 2.45 m, 1H), 2.35-2.09 (m, 1H), 1.76-1.58 (m, 1H), 1.48-1.35 (m,2H), 1.27-1.19 (m, 2H), 1.19-1.13 (m, 2H), 1.06-0.92 (m, 1H), 0.92-0.72(m, 3H) 221C J 603 (M + H) 113 (dec) (400 MHz, CDCl₃) δ 8.56 (s, 1H),8.20-8.10 (m, 2H), 8.00 (s, 1H), 7.83-7.77 (m, 2H), 7.75 (d, J = 8.4 Hz,2H), 7.42-7.28 (m, 6H), 6.72-6.25 (m, 1H), 3.90 (d, J = 6.4 Hz, 1H),3.24 (td, J = 12.0, 3.6 Hz, 1H), 3.05-2.93 (m, 1H), 2.49 (tt, J = 11.7,4.0 Hz, 1H), 2.21 (td, J = 8.7, 4.4 Hz, 1H), 1.29 (d, J = 6.6 Hz, 3H)222C J 594 (M + H) 124 (dec) (CDCl₃) δ 8.55 (s, 1H), 8.14 (dd, J = 8.4,2.1 Hz, 2H), 8.05 (d, J = 2.8 Hz, 1H), 7.87-7.72 (m, 4H), 7.61-7.49 (m,1H), 7.38 (d, J = 8.3 Hz, 2H), 7.33-7.21 (m, 2H), 7.15-7.05 (m, 1H),3.79-3.68 (m, 1H), 3.51-3.29 (m, 1H), 3.12-2.93 (m, 1H), 2.66-2.52 (m,1H), 2.18-2.12 (m, 1H), 1.43 (m, 12H) 223C L 566 (M + H) 75-87 (CDCl₃) δ8.58 (s, 1H), 8.21 (d, J = 8.4 Hz, 2H), 8.16 (s, 1H), 7.85-7.77 (m, 4H),7.40 (d, J = 8.3 Hz, 2H), 7.23 (dd, J = 8.4, 6.6 Hz, 1H), 7.15 (d, J =7.5 Hz, 2H), 3.24-3.14 (m, 4H), 2.18 (s, 6H). 224C L 580 (M + H) 118(dec) (CDCl₃) δ 8.57 (s, 1H), 8.21 (d, J = 8.4 Hz, 2H), 8.16 (s, 1H),7.85-7.75 (m, 4H), 7.46-7.36 (m, 4H), 7.33-7.26 (m, 1H), 7.10 (d, J =7.6 Hz, 1H), 3.26-3.14 (m, 4H), 2.81 (sept, J = 6.9 Hz, 1H), 1.21 (t, J= 7.2 Hz, 6H). 225C L 580 (M + H) 111 (dec) (CDCl₃) δ 8.57 (s, 1H), 8.21(d, J = 8.4 Hz, 2H), 8.15 (s, 1H), 7.86-7.76 (m, 4H), 7.39 (d, J = 8.3Hz, 2H), 7.29 (t, J = 7.6 Hz, 1H), 7.21-7.15 (m, 2H), 3.27-3.10 (m, 4H),2.50 (q, J = 7.5 Hz, 2H), 2.18 (s, 3H), 1.20 (t, J = 7.6 Hz, 3H). 226C L573 (M + H) 196-200 (CDCl₃) δ 8.57 (s, 1H), 8.24-8.16 (m, 3H), 7.85-7.76(m, 4H), 7.43-7.34 (m, 3H), 7.03 (dd, J = 8.5, 7.4 Hz, 2H), 3.21 (s, 4H)227C L 586 (M + H) Oil (CDCl₃) δ 8.57 (s, 1H), 8.21 (d, J = 8.3 Hz, 2H),8.15 (s, 1H), 7.81 (t, J = 9.1 Hz, 4H), 7.43-7.31 (m, 3H), 7.28-7.21 (m,2H), 3.36-3.07 (m, 4H), 2.24 (s, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ −58.02228C L 640 (M + H)  99 (dec) (CDCl₃) δ 8.57 (s, 1H), 8.21 (d, J = 8.3Hz, 2H), 8.11 (s, 1H), 7.81 (dd, J = 11.5, 4.7 Hz, 4H), 7.72 (dd, J =17.3, 8.0 Hz, 2H), 7.51 (dd, J = 10.0, 5.4 Hz, 1H), 7.39 (d, J = 8.3 Hz,2H), 3.36-3.03 (m, 4H) 229C L 622 (M + H)  95 (dec) (CDCl₃) δ 8.57 (s,1H), 8.21 (d, J = 8.4 Hz, 2H), 8.13 (s, 1H), 7.80 (dt, J = 5.5, 4.9 Hz,4H), 7.44-7.34 (m, 6H), 3.29-3.10 (m, 4H) 230C L 594 (M + H)  94 (dec)(CDCl₃) δ 8.57 (s, 1H), 8.21 (d, J = 8.3 Hz, 2H), 8.14 (d, J = 15.4 Hz,1H), 7.83-7.76 (m, 4H), 7.43-7.37 (m, 4H), 7.32-7.26 (m, 1H), 7.16-7.09(m, 1H), 3.24-3.12 (m, 4H), 2.61-2.44 (m, 1H), 1.75-1.50 (m, 2H), 1.17(dd, J = 6.9, 3.3 Hz, 3H), 0.87-0.73 (m, 3H) 231C L 582 (M + H) 105(dec) (CDCl₃) δ 8.58 (s, 1H), 8.22 (s, 1H), 8.19 (d, J = 5.0 Hz, 2H),7.81 (dd, J = 8.7, 5.5 Hz, 4H), 7.40 (d, J = 8.3 Hz, 2H), 7.05 (d, J =8.3 Hz, 1H), 6.90-6.76 (m, 2H), 3.83 (s, 3H), 3.22-3.11 (m, 4H), 2.16(s, 3H) 232C L 593 (M + H) 120 (dec) (CDCl₃) δ 8.57 (s, 1H), 8.21 (d, J= 8.4 Hz, 2H), 8.16 (s, 1H), 7.81 (dd, J = 8.7, 5.3 Hz, 4H), 7.58 (dd, J= 8.1, 1.5 Hz, 1H), 7.38 (dd, J = 13.2, 5.1 Hz, 3H), 7.33-7.27 (m, 1H),7.02-6.96 (m, 1H), 3.37-3.01 (m, 4H), 1.36 (s, 9H) 233C L 604 (M + H) 92 (dec) (CDCl₃) δ 8.58 (s, 1H), 8.21 (d, J = 8.4 Hz, 2H), 8.14 (s,1H), 7.86-7.72 (m, 4H), 7.48-7.28 (m, 6H), 6.40 (t, J_(HF) = 74.3 Hz,1H), 3.25-3.11 (m, 4H) 240C M 576 (M + H) 105 (dec) (CDCl₃) δ 8.57 (s,1H), 8.25-8.12 (m, 3H), 7.88-7.72 (m, 4H), 7.39 (d, J = 8.5 Hz, 3H),7.06 (td, J = 8.9, 4.4 Hz, 2H), 3.58 (d, J = 11.5 Hz, 1H), 3.37 (d, J =11.5 Hz, 1H), 3.24 (d, J = 2.7 Hz, 1H), 1.59 (s, 3H); ¹⁹F NMR (376 MHz,CDCl₃) δ −58.02, −113.71, −115.83, −115.84 241C M 642 (M + H)  97 (dec)(CDCl₃) δ 9.72-9.57 (m, 1H), 8.58 (s, 1H), 8.24 (d, J = 8.4 Hz, 2H),7.88-7.72 (m, 4H), 7.56 (dt, J = 18.3, 5.8 Hz, 2H), 7.40 (d, J = 8.3 Hz,2H), 7.09 (t, J = 8.0 Hz, 1H), 3.49 (d, J = 13.3 Hz, 1H), 3.35 (m, 2H),1.86 (d, J = 14.0 Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ −58.01, −62.05,−62.22 242C M 582 (M + H) 114-116 (CDCl₃) δ 8.57 (s, 1H), 8.19 (dd, J =10.1, 6.2 Hz, 3H), 7.79 (dd, J = 11.5, 4.7 Hz, 4H), 7.50-7.44 (m, 1H),7.44-7.36 (m, 4H), 7.29-7.25 (m, 1H), 3.55 (d, J = 11.5 Hz, 1H), 3.45(s, 1H), 3.34 (d, J = 11.5 Hz, 1H), 2.98 (dt, J = 13.8, 6.9 Hz, 1H),1.43 (s, 3H), 1.27-1.16 (m, 6H); ¹⁹F NMR (376 MHz, CDCl₃) δ −58.02 243CM 596 (M + H) 112 (dec) (CDCl₃) δ 8.57 (s, 1H), 8.23-8.13 (m, 3H),7.84-7.74 (m, 4H), 7.55-7.44 (m, 1H), 7.43-7.32 (m, 4H), 7.28-7.24 (m,1H), 3.55-3.51 (m, 2H), 3.32 (dd, J = 11.5, 1.0 Hz, 1H), 2.69 (td, J =13.9, 7.0 Hz, 1H), 1.63-1.56 (m, 2H), 1.45 (d, J = 4.9 Hz, 3H),1.26-1.16 (m, 3H), 0.83 (dt, J = 10.2, 7.4 Hz, 3H); ¹⁹F NMR (376 MHz,CDCl₃) δ −58.02 244C M 588 (M + H) 103 (dec) (CDCl₃) δ 8.57 (s, 1H),8.22 (s, 1H), 8.18 (d, J = 8.4 Hz, 2H), 7.83-7.76 (m, 4H), 7.41-7.32 (m,3H), 7.25-7.21 (m, 2H), 3.70-3.61 (m, 1H), 3.53 (s, 1H), 3.30 (d, J =11.2 Hz, 1H), 2.49 (s, 3H), 1.51 (s, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ−58.02 245C M 584 (M + H) 129 (dec) (CDCl₃) δ 8.57 (s, 1H), 8.25 (s,1H), 8.18 (d, J = 8.3 Hz, 2H), 7.82-7.75 (m, 4H), 7.39 (t, J = 8.8 Hz,3H), 6.86-6.76 (m, 2H), 3.83 (s, 3H), 3.52 (d, J = 11.5 Hz, 1H), 3.43(s, 1H), 3.31 (d, J = 11.6 Hz, 1H), 2.19 (s, 2H), 1.43 (s, 3H); ¹⁹F NMR(376 MHz, CDCl₃) δ −58.02 246C M 636 (M + H) 185-187 (CDCl₃, bothdiastereomers) δ 8.56 (m, 2H), 8.22-8.14 (m, 6H), 7.83-7.75 (m, 8H),7.49-7.34 (m, 10H), 7.32-7.23 (m, 2H), 4.22 (s, 1H), 3.82 (dd, J = 12.5,4.8 Hz, 2H), 3.51 (d, J = 13.2 Hz, 1H), 3.40 (d, J = 12.3 Hz, 1H), 3.31(s, 1H), 3.09 (tt, J = 13.9, 7.0 Hz, 2H), 1.31-1.13 (m, 12H); ¹⁹F NMR(376 MHz, CDCl₃) δ −58.02, −78.33, −78.77 247C M 650 (M + H) — (CDCl₃) δ8.59-8.54 (m, 1H), 8.30-8.13 (m, 3H), 7.79 (dd, J = 8.6, 6.7 Hz, 4H),7.45-7.34 (m, 5H), 7.32-7.21 (m, 1H), 3.99 (s, 1H), 3.83 (d, J = 12.2Hz, 1H), 3.52-3.38 (m, 1H), 2.82-2.75 (m, 1H), 1.27-1.26 (m, 1H),1.21-1.12 (m, 3H), 0.97-0.75 (m, 4H); ¹⁹F NMR (376 MHz, CDCl₃) δ −58.03,−78.23, −78.32, −78.76, −78.84 248C M 554 (M + H) 113-126 (CDCl₃) δ 8.57(d, J = 2.3 Hz, 1H), 8.24 (s, 1H), 8.18 (d, J = 8.3 Hz, 2H), 7.83-7.74(m, 4H), 7.54-7.47 (m, 1H), 7.39-7.27 (m, 5H), 3.66 (s, 1H), 3.54 (d, J= 11.5 Hz, 1H), 3.33 (d, J = 11.5 Hz, 1H), 2.41-2.18 (m, 3H), 1.60-1.41(m, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ −58.02 249C M 607 (M + H) 134 (dec)(CDCl₃) δ 8.57 (s, 1H), 8.28-8.13 (m, 3H), 7.85-7.72 (m, 4H), 7.50-7.34(m, 5H), 7.28-7.23 (m, 1H), 3.54 (d, J = 11.5 Hz, 1H), 3.42 (s, 1H),3.33 (d, J = 11.5 Hz, 1H), 3.04 (dd, J = 17.2, 9.3 Hz, 1H), 2.09 (s,1H), 1.93-1.75 (m, 3H), 1.68-1.60 (m, 3H), 1.55 (s, 3H), 1.43 (s, 2H);¹⁹F NMR (376 MHz, CDCl₃) δ −58.02 250C M 600 (M + H) 112 (dec) (CDCl₃) δ8.57 (s, 1H), 8.19-8.17 (m, 3H), 7.83-7.75 (m, 4H), 7.42-7.33 (m, 3H),7.23 (t, J = 7.0 Hz, 1H), 7.10-6.95 (m, 1H), 3.56 (dd, J = 30.7, 11.4Hz, 1H), 3.44-2.90 (m, 3H), 1.54-1.48 (m, 3H), 1.27-1.15 (m, 6H); ¹⁹FNMR (376 MHz, CDCl₃) δ −58.02, −116.16, −117.35 251C M 596 (M + H) 118(CDCl₃) δ 8.57 (s, 1H), 8.23 (s, 1H), 8.20-8.14 (m, 2H), 7.83-7.72 (m,4H), 7.39-7.33 (m, 3H), 7.20 (s, 1H), 7.10-7.05 (m, 1H), 3.53 (d, J =11.5 Hz, 1H), 3.43 (s, 1H), 3.32 (d, J = 11.5 Hz, 1H), 2.98-2.88 (m,1H), 2.39 (s, 3H), 1.43 (s, 3H), 1.28-1.14 (m, 6H); ¹⁹F NMR (376 MHz,CDCl₃) δ −58.03 252C M 596 (M + H) 118 (dec) (CDCl₃) δ 8.57 (s, 1H),8.22 (s, 1H), 8.18 (d, J = 8.4 Hz, 2H), 7.81-7.77 (m, 4H), 7.38 (d, J =8.4 Hz, 2H), 7.33 (t, J = 4.7 Hz, 1H), 7.17 (d, J = 5.0 Hz, 2H), 3.53(d, J = 11.5 Hz, 1H), 3.42 (s, 1H), 3.37-3.18 (m, 2H), 2.52 (s, 3H),1.42 (s, 3H), 1.32 (dd, J = 7.3, 3.7 Hz, 6H); ¹⁹F NMR (376 MHz, CDCl₃) δ−58.02 253C M 596 (M + H) 112 (dec) (CDCl₃) δ 8.57 (s, 1H), 8.23 (s,1H), 8.21-8.15 (m, 2H), 7.79 (t, J = 8.1 Hz, 4H), 7.38 (d, J = 8.9 Hz,2H), 7.31-7.27 (m, 2H), 7.21 (d, J = 8.1 Hz, 1H), 3.53 (d, J = 11.5 Hz,1H), 3.44 (s, 1H), 3.33 (d, J = 11.5 Hz, 1H), 2.91 (dt, J = 13.8, 6.9Hz, 1H), 2.34 (d, J = 3.1 Hz, 3H), 1.59-1.43 (m, 3H), 1.19 (dd, J =10.4, 6.9 Hz, 6H); ¹⁹F NMR (376 MHz, CDCl₃) δ −58.02 254C M 568 (M + H)111 (dec) (CDCl₃) δ 8.57 (s, 1H), 8.23 (s, 1H), 8.21-8.15 (m, 2H),7.83-7.74 (m, 4H), 7.50 (d, J = 7.7 Hz, 1H), 7.39 7.37 (m, 4H),7.31-7.27 (m, 1H), 3.54 (d, J = 11.5 Hz, 1H), 3.47 (s, 1H), 3.32 (d, J =11.5 Hz, 1H), 2.68-2.45 (m, 2H), 1.43 (s, 3H), 1.28-1.21 (m, 3H); ¹⁹FNMR (376 MHz, CDCl₃) δ −58.02 255C M 597 (M + H) 110 (dec) (CDCl₃) δ8.57 (s, 1H), 8.25 (s, 1H), 8.18 (d, J = 8.3 Hz, 2H), 7.84-7.75 (m, 4H),7.39 (d, J = 8.3 Hz, 2H), 6.76-6.64 (m, 2H), 3.80 (s, 3H), 3.51 (d, J =11.3 Hz, 1H), 3.35 (s, 1H), 3.32 (d, J = 11.4 Hz, 1H), 2.40 (s, 3H),2.14 (s, 3H), 1.43 (s, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ −58.02 256C M 580(M + H) 100 (CDCl₃) δ 8.57 (s, 1H), 8.24-8.15 (m, 3H), 7.79 (dd, J =8.8, 2.7 Hz, 4H), 7.51 (d, J = 7.6 Hz, 1H), 7.40-7.33 (m, 4H), 7.30-7.28(m, 1H), 3.64 (s, 1H), 3.54 (d, J = 11.5 Hz, 1H), 3.32 (d, J = 11.5 Hz,1H), 2.60-2.40 (m, 2H), 1.76-1.62 (m, 2H), 1.43 (s, 3H), 0.94 (t, J =7.3 Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ −58.02 257C M 595 (M + H) 140(dec) (CDCl₃) δ 8.57 (s, 1H), 8.22-8.16 (m, 3H), 7.82-7.74 (m, 4H),7.55-7.47 (m, 1H), 7.42-7.35 (m, 4H), 7.29-7.24 (m, 1H), 3.92-2.96 (m,3H), 1.57 (s, 1H), 1.57-1.50 (m, 3H), 1.35-1.17 (m, 9H); ¹⁹F NMR (376MHz, CDCl₃) δ −58.02 258C M 597 (M − H) 117 (dec) (CDCl₃) δ 8.57 (s,1H), 8.22-8.16 (m, 3H), 7.80 (dt, J = 8.4, 4.9 Hz, 4H), 7.46 (dd, J =8.8, 5.6 Hz, 1H), 7.39 (d, J = 8.3 Hz, 2H), 7.09 (dd, J = 10.0, 2.9 Hz,1H), 7.01-6.90 (m, 1H), 3.54 (d, J = 11.5 Hz, 1H), 3.39 (s, 1H), 3.33(d, J = 11.6 Hz, 1H), 2.99-2.92 (m, 1H), 1.56 (d, J = 7.3 Hz, 3H), 1.42(s, 3H), 1.20 (dd, J = 8.6, 6.9 Hz, 6H); ¹⁹F NMR (376 MHz, CDCl₃) δ−58.02, −112.57 259C M 615 (M − H) 186-188 (CDCl₃) δ 8.57 (s, 1H), 8.21(d, J = 3.5 Hz, 2H), 8.18 (s, 1H), 7.83-7.75 (m, 4H), 7.43-7.34 (m, 3H),7.17 (dd, J = 11.8, 8.6 Hz, 1H), 3.54 (d, J = 11.6 Hz, 1H), 3.44 (s,1H), 3.32 (d, J = 11.6 Hz, 1H), 2.93 (dd, J = 13.0, 6.1 Hz, 1H), 1.45(s, 3H), 1.18 (dd, J = 14.2, 6.9 Hz, 6H); ¹⁹F NMR (376 MHz, CDCl₃) δ−58.02, −136.51, −136.57, −138.80, −138.86 260C M 665 (M + H) 117 (dec)(CDCl₃) δ 8.66 (s, 1H), 8.24-8.15 (m, 3H), 7.93 (d, J = 8.8 Hz, 2H),7.78 (dd, J = 8.2, 6.5 Hz, 4H), 7.52-7.45 (m, 1H), 7.45-7.36 (m, 2H),7.29-7.25 (m, 1H), 3.55 (d, J = 7.5 Hz, 1H), 3.50 (s, 1H), 3.34 (d, J =11.5 Hz, 1H), 3.01-2.95 (m, 1H), 1.21 (dd, J = 8.3, 7.0 Hz, 6H); ¹⁹F NMR(376 MHz, CDCl₃) δ −75.61, −182.14, −182.16, −182.18 261C M 565 (M + H)113 (dec) (CDCl₃) δ 8.66 (s, 1H), 8.22-8.19 (m, 2H), 8.18 (s, 1H), 7.91(d, J = 8.4 Hz, 2H), 7.79 (d, J = 8.4 Hz, 4H), 7.50-7.44 (m, 1H),7.44-7.36 (m, 2H), 7.29-7.25 (m, 1H), 3.55 (d, J = 11.5 Hz, 1H), 3.50(s, 1H), 3.34 (d, J = 11.5 Hz, 1H), 3.04-2.91 (m, 1H), 1.21 (dd, J =8.3, 6.9 Hz, 6H); ¹⁹F NMR (376 MHz, CDCl₃) δ −62.50 262C M 631 (M + H)115 (dec) (CDCl₃) δ 8.58 (s, 1H), 8.19 (dd, J = 8.5, 6.8 Hz, 3H), 7.80(dd, J = 12.5, 5.3 Hz, 4H), 7.50-7.44 (m, 1H), 7.42-7.36 (m, 4H),7.29-7.24 (m, 1H), 3.53 (dd, J = 14.9, 11.4 Hz, 2H), 3.34 (d, J = 11.5Hz, 1H), 3.03-2.89 (m, 1H), 1.21 (dd, J = 8.4, 6.9 Hz, 6H); ¹⁹F NMR (376MHz, CDCl₃) δ −85.90, −87.85 263C M 711 (M + H) 115.3-117.6 (CDCl₃) δ8.59 (s, 1H), 8.33 (s, 1H), 8.24 (d, J = 8.4 Hz, 2H), 8.13 (s, 1H),7.86-7.77 (m, 5H), 7.73 (d, J = 7.2 Hz, 1H), 7.62 (dt, J = 21.6, 7.2 Hz,2H), 7.40 (d, J = 8.2 Hz, 2H), 7.37-7.28 (m, 3H), 7.24-7.17 (m, 1H),4.34 (s, 2H), 3.20 (dt, J = 13.7, 6.8 Hz, 2H), 1.25 (d, J = 6.9 Hz, 6H);¹⁹F NMR (376 MHz, CDCl₃) δ −58.02 264C M 647 (M + H) 116-120 (300 MHz,CDCl₃) δ 8.57 (s, 1H), 8.23 (d, J = 4.9 Hz, 1H), 8.18 (dd, J = 8.3, 1.7Hz, 2H), 7.84-7.75 (m, 4H), 7.39 (dd, J = 8.8, 6.8 Hz, 3H), 6.89 (d, J =3.0 Hz, 1H), 6.80 (dd, J = 8.6, 3.1 Hz, 1H), 3.84 (s, 3H), 3.51 (d, J =11.6 Hz, 1H), 3.48-3.43 (m, 1H), 3.31 (d, J = 11.5 Hz, 1H), 2.65-2.40(m, 2H), 1.41 (s, 3H), 1.22 (t, J = 7.6 Hz, 3H) NMR spectral data wereacquired using a 400 MHz instrument except where noted.

TABLE 4A Analytical Data for Optically Active Compounds in Table 3Chiral Separation Purity ID Method MS (%) ¹H NMR (δ)¹ 234C A 571 (M + H)98.73 (CDCl₃) δ 8.58 (s, 1H), 8.31 (s, 1H), 8.23 (d, J = 8.4 Hz, 2H),7.87-7.78 (m, 4H), 7.41 (t, J = 6.3 Hz, 3H), 7.37-7.31 (m, 1H), 7.28 (d,J = 7.0 Hz, 1H), 4.09-3.98 (m, 2H), 2.29 (s, 3H) 235C A 571 (M + H)95.75 (CDCl₃) δ 8.58 (s, 1H), 8.31 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H),7.87-7.78 (m, 4H), 7.41 (dd, J = 7.0, 5.6 Hz, 3H), 7.34 (t, J = 7.8 Hz,1H), 7.28 (d, J = 6.0 Hz, 1H), 4.09-3.98 (m, 2H), 2.29 (s, 3H) 236C A565 (M + H) 96.32 (CDCl₃) δ 8.58 (s, 1H), 8.31 (s, 1H), 8.23 (d, J = 8.4Hz, 2H), 7.81 (dd, J = 11.7, 5.1 Hz, 4H), 7.40 (d, J = 8.4 Hz, 2H), 7.35(t, J = 7.7 Hz, 1H), 7.24-7.18 (m, 2H), 4.02 (s, 2H), 2.53 (q, J = 7.5Hz, 2H), 2.21 (s, 3H), 1.21 (t, J = 7.6 Hz, 3H) 237C A 565 (M + H) 92.33(CDCl₃) δ 8.58 (s, 1H), 8.31 (s, 1H), 8.23 (d, J = 8.4 Hz, 2H), 7.81(dd, J = 11.7, 5.1 Hz, 4H), 7.40 (d, J = 8.3 Hz, 2H), 7.35 (dd, J =10.4, 4.9 Hz, 1H), 7.24-7.20 (m, 2H), 4.02 (s, 2H), 2.59-2.45 (m, 2H),2.21 (s, 3H), 1.21 (t, J = 7.6 Hz, 3H) 238C B 579 (M + H) 95.41 (CDCl₃)δ 8.58 (s, 1H), 8.29 (d, J = 3.9 Hz, 1H), 8.23 (d, J = 8.4 Hz, 2H), 7.82(t, J = 8.8 Hz, 4H), 7.40 (d, J = 8.3 Hz, 3H), 7.31 (d, J = 6.9 Hz, 1H),7.19 (dd, J = 7.6, 5.2 Hz, 1H), 4.03 (s, 2H), 2.83-2.73 (m, 1H), 2.21(s, 3H), 1.25-1.18 (m, 6H) 239C B 579 (M + H) 92.68 (CDCl₃) δ 8.58 (s,1H), 8.30 (s, 1H), 8.22 (t, J = 8.7 Hz, 2H), 7.82 (t, J = 8.7 Hz, 4H),7.40 (d, J = 8.2 Hz, 3H), 7.31 (d, J = 8.0 Hz, 1H), 7.20 (d, J = 7.3 Hz,1H), 4.03 (s, 2H), 2.83-2.73 (m, 1H), 2.21 (s, 3H), 1.25-1.18 (m, 6H)NMR spectral data were acquired using a 400 MHz instrument except wherenoted.

TABLE 5 Biological Results % % % Mortality Mortality Mortality CompoundCEW 50 BAW 50 GPA 200 Number μg/cm² μg/cm² ppm 1C A A D 2C A A D 3C A AD 4C A A B 5C A A B 6C A A D 7C A D D 8C A A B 9C A A D 10C A A D 11C AA D 12C A A B 13C A A B 14C A A B 15C A A A 16C A A D 17C A A B 18C A AB 19C A A B 20C A A D 21C C C D 22C A A B 23C A A D 24C A A B 25C A A D26C C C D 27C A A B 28C A A B 29C A A B 30C A A B 31C A A B 32C C C B33C A A B 34C C C B 35C A A B 36C A A D 37C A A D 38C A A D 39C C C D40C A A B 41C A A D 42C A A D 43C A A B 44C A A D 45C A A C 46C A A D47C A A B 48C A A C 49C A A B 50C A A C 51C A A D 52C D B B 53C D B B54C A A D 55C A A D 56C A A C 57C A A B 58C A A B 59C A A B 60C A A D61C A A C 62C A A B 63C A A D 64C A A D 65C A A B 66C A A B 67C A A D68C A A B 69C A A C 70C A A D 71C A A D 72C A A B 73C A A B 74C A A D75C A A B 76C A A B 77C A A B 78C A A B 79C A A B 80C A A D 81C A A D82C A A C 83C A A C 84C A A D 85C A A B 86C A A D 87C C C B 88C A A B89C A A D 90C A A B 91C D D C 92C A A B 93C A A D 94C A A D 95C A A B96C A A B 97C A A C 98C C A C 99C A A C 100C A A C 101C A A C 102C A A C103C A A C 104C A A C 105C A A C 106C A A C 107C D D C 108C A A D 109C AA C 110C A A C 111C A A B 112C A A B 113C A A C 114C A A C 115C D B C116C A A C 117C A A D 118C A A D 119C A A D 120C A A C 121C A A B 122C AA C 123C A A C 124C A A C 125C A A C 126C A A C 127C A A C 128C A A C129C A A C 130C A A C 131C A A D 132C A A B 133C A A B 134C A A C 135C AA D 136C A A D 137C A A D 138C A A B 139C A A B 140C A A B 141C A A D142C A A D 143C A A C 144C A A C 145C A A B 146C A A B 147C A A B 148C AA C 149C A A D 150C A A D 151C A A B 152C A A C 153C A d C 154C A A B155C A A D 156C A A B 157C A A B 158C A A B 159C A A C 160C A A C 161C AA C 162C A A C 163C A A C 164C A A C 165C A A C 166C A A C 167C A A C168C A A D 169C A A C 170C A A C 171C A A C 172C A A D 173C A A D 174C AA B 175C A A D 176C A A C 177C A A D 178C A A D 179C A A D 180C A A B181C A A B 182C A A B 183C A A D 184C A A D 185C A A D 186C A A B 187C AA D 188C A A B 189C A A B 190C A A B 191C A A D 192C A A B 193C A A B194C A A B 195C A A B 196C A A D 197C A A D 198C A A D 199C A A C 200C AA C 201C A A B 202C A A B 203C A A B 204C A A B 205C A A B 206C A A D207C d D C 208C A A D 209C A A D 210C A A C 211C A A D 212C A A D 213C AA B 214C A A C 215C A A C 216C A A C 217C A A C 218C A A C 219C A A C220C A A C 221C A A C 222C A A C 223C A A C 224C A A B 225C A A C 226C AA C 227C A A C 228C A A C 229C A A C 230C A A C 231C A A C 232C A A C233C A A C 234C A A C 235C A A C 236C A A C 237C A A C 238C A A C 239C AA C 240C A A D 241C A A C 242C A A B 243C A A B 244C A A D 245C A A B246C A A C 247C A A C 248C A A B 249C A A C 250C A A B 251C A A B 252C AA C 253C A A D 254C A A B 255C A A D 256C A A B 257C A A D 258C A A C259C A A D 260C A A D 261C A A D 262C A A B 263C A A B 264C C A C

We claim:
 1. A molecule according to Formula Two or Formula Three

wherein: (a) Ar₁ is a substituted phenyl wherein said substituted phenylhas one or more substituents independently selected from C₁-C₆ haloalkyland C₁-C₆ haloalkoxy; (b) Het is a 1,2,4-triazolyl

(c) Ar₂ is phenyl; (d) R1 is H or a C₁-C₆ alkyl; (g) R4 is phenylwherein said phenyl is substituted with one or more substituentsindependently selected from F, Cl, Br, I, C₁-C₆ alkyl, C₁-C₆ haloalkyl,C₃-C₆ cycloalkyl, C₁-C₆ alkoxy, and C₁-C₆ haloalkoxy; and (h) R5 is a 2to 4 membered saturated or unsaturated hydrocarbyl linkage wherein saidlinkage is substituted with at least one OH, and optionally one or moresubstituents selected from F, Cl, Br, I, C₁-C₆ alkyl, C₁-C₆ haloalkyl,and phenyl, wherein said phenyl is optionally substituted with one ormore substituents independently selected from F, Cl, Br, I, C₁-C₆ alkyl,and C₁-C₆ haloalkyl.
 2. A molecule according to claim 1 wherein Ar₁ hasone or more substituents independently selected from CF₃, OCF₃, andOCF₂CF₃.
 3. A molecule according to claim 1 wherein R1 is H or CH₃.
 4. Amolecule according to claim 1 wherein R5 has one or more substituentsselected from C₁-C₆ haloalkyl, and C₁-C₆ alkyl.
 5. A molecule accordingto claim 1 wherein said molecule is selected from


6. A process to apply a molecule according to claim 1 said processcomprising applying said molecule to an area to control a pest, in anamount sufficient to control such pest.
 7. A process according to claim6 wherein said molecule is selected from


8. A process according to claim 6 wherein said area is an area whereapples, corn, cotton, soybeans, canola, wheat, rice, sorghum, barley,oats, potatoes, oranges, alfalfa, lettuce, strawberries, tomatoes,peppers, crucifers, pears, tobacco, almonds, sugar beets, or beans, aregrowing, or the seeds thereof are going to be planted.